Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
  • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
  • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
  • C08G73/1042—Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
  • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
  • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
  • C08G73/1057—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
  • 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
  • C08G73/14—Polyamide-imides
• • 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
• • G—PHYSICS
  • G02—OPTICS
  • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
  • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
  • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
  • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
  • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
  • G02F1/1333—Constructional arrangements; Manufacturing methods
• • 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 an imide-amide acid copolymer which is a precursor of a polyimide resin, a method for producing the same, a varnish containing the copolymer, and a polyimide film.
• polyimide resins are being studied in the fields of electrical and electronic components and the like. For example, it is desired to replace a glass substrate used in an image display device such as a liquid crystal display or an OLED display with a plastic substrate for the purpose of reducing the weight and flexibility of the device. Research is underway. Polyimide films for such applications are required to have transparency and low yellowness. Further, when the varnish coated on the glass support or the silicon wafer is heat-cured to form the polyimide film, residual stress is generated in the polyimide film. If the residual stress of the polyimide film is large, there is a problem that the glass support and the silicon wafer are warped. Therefore, the polyimide film is also required to reduce the residual stress.
• Patent Document 1 describes two specific amic acid structural units for the purpose of obtaining a polyimide film having low residual stress, low warpage, low yellowness, and high elongation.
• a polyimide precursor is disclosed, which is characterized by containing the above in a specific ratio.
• a polyimide film for a specific application is required to have transparency and low yellowness.
• the process temperature exceeds 400 ° C.
• the polyimide used as the substrate is required to have heat resistance to withstand a high temperature of 400 ° C. or higher.
• it is required to maintain transparency and low yellowness.
• Patent Document 1 discloses a technique for reducing residual stress and reducing yellowness, but it is still insufficient.
• the present invention has been made in view of such a situation, and the subject of the present invention is a precursor of a polyimide resin capable of obtaining a polyimide film having low residual stress, excellent transparency, heat resistance, and low yellowness.
• An object of the present invention is to provide an imide-amidoic acid copolymer as a body, a method for producing the same, a varnish containing the copolymer, and a polyimide film.
• the present inventors have found that a copolymer containing a combination of specific structural units can solve the above-mentioned problems, and have completed the invention.
• IM imide moiety
• AM1 amic acid moiety
• AM2 amic acid moiety
• X 1 is a tetravalent alicyclic group having 4 to 39 carbon atoms, and the bonding groups are -O-, -SO 2- , -CO-, -CH 2- , -C (CH 3 ) 2 -,-. It may have at least one selected from the group consisting of C 2 H 4 O- and -S-.
• X 2 is a tetravalent aromatic group having 4 to 39 carbon atoms, and has -O-, -SO 2- , -CO-, -CH 2- , -C (CH 3 ) 2 -,-as a bonding group. It may have at least one selected from the group consisting of C 2 H 4 O- and -S-.
• Y 1 is a group represented by at least one selected from the group consisting of the following formula (2), the following general formula (3), and the following general formula (4).
• Y 2 is a group represented by the following general formula (5). s, t and u are positive integers. ) (In formula (3), Z 1 represents a single bond or a group represented by —O—.
• R independently represents a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 5 carbon atoms.
• Z 2 and Z 3 independently represent a group represented by -COO- or a group represented by -OCO-.
• R 1 , R 2 and R 3 are independent of each other. Then, it represents a monovalent organic group having 1 to 20 carbon atoms. H, i, j, and k are integers of 0 to 4).
• X 2 is a group represented by the following formula (7).
• the imide moiety (IM) has a structural unit X1A derived from tetracarboxylic dianhydride and a structural unit Y1B derived from diamine.
• the amic acid moiety (AM1) has a structural unit X2A derived from tetracarboxylic dianhydride and a structural unit Y1B derived from diamine.
• the amic acid moiety (AM2) has a structural unit X2A derived from tetracarboxylic dianhydride and a structural unit Y2B derived from diamine.
• Constituent unit X1A comprises a structural unit derived from an alicyclic tetracarboxylic dianhydride.
• Constituent unit X2A comprises a structural unit derived from aromatic tetracarboxylic dianhydride.
• the structural unit Y1B includes the structural unit (B1) derived from the diamine (b1), and the structural unit (B1) is the structural unit (B11) derived from the compound represented by the following formula (b11), the following general formula (B11). It contains at least one selected from the group consisting of a structural unit (B12) derived from the compound represented by b12) and a structural unit (B13) derived from the compound represented by the following general formula (b13).
• the imide-amide acid copolymer according to any one of the above [1] to [5], wherein the structural unit Y2B contains a structural unit (B2) derived from a compound represented by the following general formula (b2).
• Z 1 represents a single bond or a group represented by —O—.
• R independently represents a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 5 carbon atoms.
• Z 2 and Z 3 independently represent a group represented by -COO- or a group represented by -OCO-.
• R 1 , R 2 , and R 3 independently represent monovalent organic groups having 1 to 20 carbon atoms.
• h, i, j, and k are integers from 0 to 4.
• the structural unit X2A contains a structural unit (A2) derived from the aromatic tetracarboxylic dianhydride (a2).
• the structural unit (A2) is a structural unit (A21) derived from a compound represented by the following formula (a21), a structural unit (A22) derived from a compound represented by the following formula (a22), and the following formula (a23).
• the structural unit (A23) derived from the compound represented by the following formula, the structural unit (A24) derived from the compound represented by the following formula (a24), and the structural unit derived from the compound represented by the following formula (a25) ( The imide-amidoic acid copolymer according to the above [6], which comprises at least one selected from the group consisting of A25).
• m and n each independently represent an integer of 1 or more, and the sum of m and n represents an integer of 2 to 1000, where at least one of R 4 and R 5 represents a monovalent aromatic group. .)
• the structural unit X1A contains a structural unit (A1) derived from the alicyclic tetracarboxylic dianhydride (a1).
• the structural unit (A1) is a structural unit (A11) derived from a compound represented by the following formula (a11), a structural unit (A12) derived from a compound represented by the following formula (a12), and the following formula (a13).
• [12] A varnish in which the copolymer according to any one of the above [1] to [11] is dissolved in an organic solvent.
• a method for producing an imide-amidoic acid copolymer which comprises the following steps 1 and 2. Step 1: The tetracarboxylic acid component constituting the imide moiety (IM) is reacted with the diamine component to obtain an imide oligomer. Step 2: The imide oligomer obtained in Step 1 and the amic acid moiety (AM2) are formed.
• tetracarboxylic acid component and the diamine component are reacted to form an imide containing a repeating unit represented by the following formula (1), which is composed of an imide moiety (IM), an amide moiety (AM1) and an amic acid moiety (AM2).
• IM imide moiety
• AM1 amide moiety
• AM2 amic acid moiety
• X 1 is a tetravalent alicyclic group having 4 to 39 carbon atoms, and the bonding groups are -O-, -SO 2- , -CO-, -CH 2- , -C (CH 3 ) 2 -,-. It may have at least one selected from the group consisting of C 2 H 4 O- and -S-.
• X 2 is a tetravalent aromatic group having 4 to 39 carbon atoms, and has -O-, -SO 2- , -CO-, -CH 2- , -C (CH 3 ) 2 -,-as a bonding group. It may have at least one selected from the group consisting of C 2 H 4 O- and -S-.
• Y 1 is a group represented by at least one selected from the group consisting of the following formula (2), the following general formula (3), and the following general formula (4).
• Y 2 is a group represented by the following general formula (5). s, t and u are positive integers. ) (In formula (3), Z 1 represents a single bond or a group represented by —O—.
• R independently represents a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 5 carbon atoms.
• Z 2 and Z 3 independently represent a group represented by -COO- or a group represented by -OCO-.
• R 1 , R 2 and R 3 are independent of each other. Then, it represents a monovalent organic group having 1 to 20 carbon atoms. H, i, j, and k are integers of 0 to 4).
• an imide-amidic acid copolymer which is a precursor of a polyimide resin and a method for producing the same, which can obtain a polyimide film having low residual stress, excellent transparency, heat resistance, and low yellowness.
• a varnish containing the copolymer and a polyimide film can be provided.
• the imide-amide acid copolymer of the present invention contains a repeating unit composed of an imide moiety (IM), an amic acid moiety (AM1) and an amid acid moiety (AM2) represented by the following formula (1).
• IM imide moiety
• AM1 amic acid moiety
• AM2 amid acid moiety
• X 1 is a tetravalent alicyclic group having 4 to 39 carbon atoms, and the bonding groups are -O-, -SO 2- , -CO-, -CH 2- , -C (CH 3 ) 2 -,-. It may have at least one selected from the group consisting of C 2 H 4 O- and -S-.
• X 2 is a tetravalent aromatic group having 4 to 39 carbon atoms, and has -O-, -SO 2- , -CO-, -CH 2- , -C (CH 3 ) 2 -,-as a bonding group. It may have at least one selected from the group consisting of C 2 H 4 O- and -S-.
• Y 1 is a group represented by at least one selected from the group consisting of the following formula (2), the following general formula (3), and the following general formula (4).
• Y 2 is a group represented by the following general formula (5). s, t and u are positive integers. ) (In formula (3), Z 1 represents a single bond or a group represented by —O—.
• R independently represents a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 5 carbon atoms.
• Z 2 and Z 3 independently represent a group represented by -COO- or a group represented by -OCO-.
• R 1 , R 2 and R 3 are independent of each other. Then, it represents a monovalent organic group having 1 to 20 carbon atoms.
• H, i, j, and k are integers of 0 to 4).
• the imide-amidoic acid copolymer of the present invention is excellent as a raw material for a polyimide film, and the obtained polyimide film is excellent in that it has low residual stress, excellent transparency, low yellowness, and high heat resistance.
• the reason for having these characteristics is not clear, but it is considered as follows.
• the copolymer consisting of a component derived from an alicyclic tetracarboxylic acid and the above-mentioned specific diamine component has an appropriate ratio of a bulky skeleton having a trifluoromethyl group, a sulfone group or a cardo structure, and a rigid biphenyl skeleton and an ester skeleton.
• an imide-amidoic acid copolymer having a higher molecular weight than the acid can be obtained and the physical properties after film formation are excellent. Further, the imide-amidoic acid copolymer of the present invention is considered to have excellent physical properties after film formation because the imide moiety and the amic acid moiety have a specific structure.
• the imide moiety (IM) constituting the imide-amide acid copolymer of the present invention is the moiety represented by (IM) of the above formula (1).
• X 1 is a tetravalent alicyclic group having 4 to 39 carbon atoms, and as a linking group, -O-, -SO 2- , -CO-, -CH 2- , -C. (CH 3) 2 -, - it may have at least one member selected from C 2 H 4 group consisting of O- and -S-.
• the tetravalent alicyclic group means that at least two of the four carbons bonded to the imide group are carbons constituting the alicyclic, and any of the four carbons bonded to the imide group. It is preferable that the thigh is a carbon constituting an alicyclic.
• the binding group refers to a binding group that binds each alicyclic when X 1 contains two or more alicyclics.
• the linking group is not limited to these. When X 1 is an alicyclic group, the heat resistance and transparency of the polyimide are improved, and the yellowness is lowered, which is preferable.
• X 1 is obtained by removing two dicarboxylic acid anhydride portions (four carboxy group portions) from the tetracarboxylic acid dianhydride which is a raw material of the structural unit X1A derived from the tetracarboxylic acid dianhydride which will be described later. Is preferable. Among these, X 1 is more preferably a group represented by the following formula (6).
• Y 1 is a group represented by at least one selected from the group consisting of the following formula (2), the following general formula (3) and the following general formula (4).
• Z 1 represents a single bond or a group represented by —O—.
• R independently represents a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 5 carbon atoms.
• Y 1 is obtained by removing two amino group portions from the diamine which is the raw material of the structural unit Y1B derived from the diamine described later.
• the amic acid moiety (AM2) constituting the imide-amidoic acid copolymer of the present invention is the moiety represented by (AM2) of the above formula (1).
• X 2 is a tetravalent aromatic group having 4 to 39 carbon atoms, and as a linking group, -O-, -SO 2- , -CO-, -CH 2- , -C. (CH 3) 2 -, - it may have at least one member selected from C 2 H 4 group consisting of O- and -S-.
• the tetravalent aromatic group means that all four carbons bonded to the imide group are aromatic carbons.
• the linking group refers to a linking group that binds each aromatic ring when X 1 contains two or more aromatic rings. The linking group is not limited to these.
• X 2 is obtained by removing two dicarboxylic acid anhydride portions (four carboxy group portions) from the tetracarboxylic acid dianhydride which is a raw material of the constituent unit X2A derived from the tetracarboxylic acid dianhydride which will be described later. Is preferable. Among these, X 2 is more preferably a group represented by the following formula (7).
• Y 2 is a group represented by the following general formula (5).
• Z 2 and Z 3 independently represent a group represented by -COO- or a group represented by -OCO-.
• R 1 , R 2 and R 3 are independent of each other. Then, it represents a monovalent organic group having 1 to 20 carbon atoms.
• H, i, j, and k are integers of 0 to 4).
• Y 2 is obtained by removing two amino group portions from the diamine which is the raw material of the constituent unit Y 2B derived from the diamine described later.
• the amic acid moiety (AM1) constituting the imide-amidoic acid copolymer of the present invention is the moiety represented by (AM1) of the above formula (1).
• the amic acid moiety (AM1) is a bonding moiety between the imide moiety (IM) and the amic acid moiety (AM2), and X 2 in the amic acid moiety (AM1) is the same as that of the amid acid moiety (AM2).
• Y 1 in the moiety (AM1) is similar to the imide moiety (IM).
• s is the number of repeating units of the imide moiety (IM) and is a positive integer. From the viewpoint of transparency, low yellowness, and high heat resistance, s is preferably 1 to 50, more preferably 1 to 15, further preferably 1 to 10, and 1 to 5. It is even more preferable to have.
• the average number of repetitions of the imide moiety (IM), that is, the average value of s is preferably 1 to 10, more preferably 1.5 to 9, and even more preferably 1.5 to 8. It is even more preferably 1.7 to 5.
• the average number of repetitions of the imide portion (IM) refers to the average number of repetitions of the imide portion (IM) of all the imide-amidoic acid copolymers contained in the polyimide varnish and the polyimide film described later, and is the average value of s.
• the average value refers to the average value of s of all the imide-amidic acid copolymers contained in the polyimide varnish and the polyimide film described later.
• t is the number of repeating units of the amic acid moiety (AM2) and is a positive integer. From the viewpoints of high heat resistance, low residual stress and low coefficient of linear thermal expansion, t is preferably 1 to 50, more preferably 1 to 15, and even more preferably 1 to 10. It is even more preferable that the value is ⁇ 5.
• the average number of repetitions of the amic acid moiety (AM2), that is, the average value of t is preferably 1 to 10, more preferably 1.5 to 9, and further preferably 1.5 to 8. It is preferably 1.7 to 5, and even more preferably 1.7 to 5.
• the average number of repetitions of the amic acid moiety refers to the average number of repetitions of the amic acid moiety (AM2) of all the imide-amidoic acid copolymers contained in the polyimide varnish and the polyimide film described later.
• the average value of t refers to the average value of t of all the imide-amidic acid copolymers contained in the polyimide varnish and the polyimide film described later.
• u is a number of repeating units composed of an imide moiety (IM), an amic acid moiety (AM1) and an amid acid moiety (AM2), and is a positive integer.
• u is preferably 5 to 200, more preferably 6 to 150, and even more preferably 10 to 120, from the viewpoint of heat resistance, low residual stress, and low coefficient of linear thermal expansion.
• the average number of repeating units consisting of the imide moiety (IM), the amic acid moiety (AM1) and the amic acid moiety (AM2), that is, the average value of u is preferably 5 to 200.
• the average number of repetitions of the repeating unit composed of the imide moiety (IM), the amic acid moiety (AM1) and the amic acid moiety (AM2) is the total number of iterations of all the imide-amide acid copolymers contained in the polyimide varnish and the polyimide film described later.
• the average value of the number of repetitions of the repeating unit consisting of the imide portion (IM), the amic acid moiety (AM1) and the amic acid moiety (AM2) of the above, and the average value of u is the polyimide varnish or polyimide film described later. It refers to the average value of u of all the included imide-amidic acid copolymers.
• the total ratio of the imide moiety (IM), the amic acid moiety (AM1) and the amic acid moiety (AM2) to the imide-amide acid copolymer is preferably 80% by mass or more, more preferably 82% by mass or more, and further. It is preferably 85% by mass or more, and the upper limit is not limited and is 100% by mass or less.
• the imide moiety and the amic acid moiety are randomly present, whereas in the imide-amide acid copolymer of the present invention, the imide moiety (IM) and the amic acid moiety (imide moiety (IM) and the amic acid moiety ( It is considered that the AM1) and the amic acid moiety (AM2) have a specific structure, so that the residual stress is low and the transparency, low yellowness, and heat resistance are excellent.
• the imide-amide acid copolymer of the present invention contains a repeating unit represented by the above formula (1), which is composed of an imide moiety (IM), an amic acid moiety (AM1) and an amid acid moiety (AM2).
• IM imide moiety
• AM1 amic acid moiety
• AM2 amid acid moiety
• the imide moiety (IM) has a structural unit X1A derived from tetracarboxylic acid dianhydride and a structural unit Y1B derived from diamine.
• the amic acid moiety (AM1) has a structural unit X2A derived from tetracarboxylic dianhydride and a structural unit Y1B derived from diamine.
• the amic acid moiety (AM2) has a structural unit X2A derived from tetracarboxylic dianhydride and a structural unit Y2B derived from diamine.
• Constituent unit X1A comprises a structural unit derived from an alicyclic tetracarboxylic dianhydride.
• Constituent unit X2A comprises a structural unit derived from aromatic tetracarboxylic dianhydride.
• the structural unit Y1B includes the structural unit (B1) derived from the diamine (b1), and the structural unit (B1) is the structural unit (B11) derived from the compound represented by the following formula (b11), the following general formula (B11). It contains at least one selected from the group consisting of a structural unit (B12) derived from the compound represented by b12) and a structural unit (B13) derived from the compound represented by the following general formula (b13).
• the structural unit Y2B contains a structural unit (B2) derived from the compound represented by the following general formula (b2).
• Z 1 represents a single bond or a group represented by —O—.
• R independently represents a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 5 carbon atoms.
• Z 2 and Z 3 independently represent a group represented by -COO- or a group represented by -OCO-.
• R 1 , R 2 , and R 3 independently represent monovalent organic groups having 1 to 20 carbon atoms.
• h, i, j, and k are integers from 0 to 4.
• the structural unit X1A is a structural unit derived from the tetracarboxylic dianhydride occupying the imide moiety (IM) of the copolymer of the present invention, and includes a structural unit derived from the alicyclic tetracarboxylic dianhydride. ..
• the structural unit X1A is not limited as long as it contains a structural unit derived from an alicyclic tetracarboxylic dianhydride, but the structural unit X1A is derived from an alicyclic tetracarboxylic dianhydride (a1). It is preferable to include the structural unit (A1) to be used.
• the structural unit (A1) is a structural unit (A11) derived from a compound represented by the following formula (a11), a structural unit (A12) derived from a compound represented by the following formula (a12), and the following. It contains at least one selected from the group consisting of structural units (A13) derived from the compound represented by the formula (a13).
• the compound represented by the formula (a11) is norbornane-2-spiro- ⁇ -cyclopentanone- ⁇ '-spiro-2''-norbornane-5,5'', 6,6''-tetracarboxylic dianhydride. It is an anhydride (CpODA).
• the compound represented by the formula (a12) is 5,5'-(1,4-phenylene) -bis [hexahydro-4,7-Methanoisobenzofuran-1,3-dione] (BzDA).
• the compound represented by the formula (a13) is 5,5'-bis-2-norbornene-5,5', 6,6'-tetracarboxylic acid-5,5', 6,6'-dianhydride ( BNBDA).
• the structural unit (A1) more preferably includes the structural unit (A11) from the viewpoint of heat resistance, transparency, and low yellowness.
• the total ratio of the constituent units (A11) to (A13) in the constituent unit (A1) is preferably 45 mol% or more, more preferably 70 mol% or more, still more preferably 90 mol% or more, and particularly preferably 99. More than mol%.
• the upper limit of the ratio is not particularly limited and is 100 mol% or less.
• the structural unit (A1) may include at least one type selected from the structural units (A11) to (A13), and is composed of only one type selected from the structural units (A11) to (A13). May be good.
• the ratio of the constituent unit (A11) in the constituent unit (A1) is preferably 45 mol% or more, more preferably 70 mol% or more, still more preferably 90 mol% or more, and particularly preferably 99 mol% or more. ..
• the upper limit of the ratio is not particularly limited and is 100 mol% or less.
• the structural unit (A1) may have a structural unit derived from an alicyclic tetracarboxylic dianhydride other than the compounds represented by the formulas (a11) to (a13).
• alicyclic tetracarboxylic acid dianhydride examples include 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 1,2,3,4-cyclopentanetetracarboxylic acid dianhydride, 1,2, 4,5-Cyclohexanetetracarboxylic acid dianhydride, bicyclo [2.2.2] octa-7-ene-2,3,5,6-tetracarboxylic acid dianhydride, dicyclohexyltetracarboxylic acid dianhydride, etc.
• 1, 2, 4, 5 are the structural units derived from the alicyclic tetracarboxylic dianhydride other than the compounds represented by the formulas (a11) to (a13) in the structural unit (A1).
• -A structural unit derived from cyclohexanetetracarboxylic dianhydride is preferred.
• the alicyclic tetracarboxylic dianhydride (a1) may be used alone or in combination of two or more.
• the ratio of the constituent unit (A1) in the constituent unit X1A is preferably 45 mol% or more, more preferably 70 mol% or more, still more preferably 90 mol% or more, and particularly preferably 99 mol% or more.
• the upper limit of the ratio is not particularly limited and is 100 mol% or less.
• the structural unit X1A may include a structural unit other than the structural unit (A1).
• the tetracarboxylic acid dianhydride giving such a constituent unit is not particularly limited, but is an aliphatic such as aromatic tetracarboxylic acid dianhydride and 1,2,3,4-butanetetracarboxylic acid dianhydride. Tetracarboxylic acid dianhydride can be mentioned.
• the alicyclic tetracarboxylic dianhydride is an acid anhydride (two adjacent carboxys) of at least one of the four ⁇ -carbons of the two acid anhydrides (four carboxy groups).
• the two ⁇ -carbons of the group) mean tetracarboxylic acid dianhydride, which is the carbon constituting the alicyclic, and the aromatic tetracarboxylic acid dianhydride is 4 of the two acid anhydrides (4 carboxy groups).
• Tetracarboxylic acid dianhydride in which one ⁇ carbon is a carbon constituting an aromatic ring means tetracarboxylic acid dianhydride
• aliphatic tetracarboxylic acid dianhydride means alicyclic tetracarboxylic acid dianhydride as well as aromatic tetracarboxylic dianhydride. It means tetracarboxylic dianhydride which does not correspond to anhydride.
• the structural unit arbitrarily included in the structural unit X1A may be one type or two or more types.
• the structural unit X2A is a structural unit derived from the tetracarboxylic acid dianhydride occupying the amic acid moiety (AM2) and the amic acid moiety (AM1) of the copolymer of the present invention, and is an aromatic tetracarboxylic acid dianhydride. Includes building blocks derived from.
• the structural unit X2A is not limited as long as it contains a structural unit derived from the aromatic tetracarboxylic dianhydride, but the structural unit X2A is a configuration derived from the aromatic tetracarboxylic dianhydride (a2). It is preferable to include the unit (A2).
• the structural unit (A2) is a structural unit (A21) derived from a compound represented by the following formula (a21), a structural unit (A22) derived from a compound represented by the following formula (a22), and the following formula.
• the compound represented by the formula (a21) is biphenyltetracarboxylic dianhydride (BPDA), and specific examples thereof include 3,3', 4,4'-biphenyl represented by the following formula (a21s).
• BPDA biphenyltetracarboxylic dianhydride
• Examples thereof include 2,2', 3,3'-biphenyltetracarboxylic dianhydride (i-BPDA) represented.
• s-BPDA 3,3', 4,4'-biphenyltetracarboxylic dianhydride represented by the following formula (a21s) is preferable.
• the compound represented by the formula (a22) is p-phenylenebis (trimeritate) dianhydride (TAHQ).
• the compound represented by the formula (a23) is an oxydiphthalic anhydride (ODPA), and specific examples thereof include 4,4′-oxydiphthalic anhydride (s-ODPA) represented by the following formula (a23s). , 3,4'-oxydiphthalic anhydride (a-ODPA) represented by the following formula (a23a), 3,3′-oxydiphthalic anhydride (i-ODPA) represented by the following formula (a23i), and the like. Be done. Of these, 4,4'-oxydiphthalic anhydride (s-ODPA) represented by the following formula (a23s) is preferable.
• the compound represented by the formula (a24) is pyromellitic acid dianhydride (PMDA).
• the compound represented by the formula (a25) is 2,3,6,7-naphthalenetetracarboxylic dianhydride.
• the constituent unit (A2) preferably includes at least one selected from the group consisting of the constituent unit (A21) and the constituent unit (A22) from the viewpoint of high heat resistance and low residual stress, and the constituent unit (A21). ) Is more preferable.
• the structural unit (A21) is preferable from the viewpoint of improving the heat resistance and thermal stability of the film and further reducing the residual stress
• the structural unit (A22) is preferable from the viewpoint of being able to reduce the residual stress. Is preferable.
• the structural unit X2A may include a structural unit other than the structural unit (A2).
• the tetracarboxylic dianhydride giving such a constituent unit is not particularly limited, but is an alicyclic tetracarboxylic dianhydride, and a fat such as 1,2,3,4-butanetetracarboxylic dianhydride.
• Group tetracarboxylic dianhydrides can be mentioned.
• the structural unit arbitrarily included in the structural unit X2A may be one type or two or more types.
• the total ratio of the constituent units (A21) to (A25) in the constituent unit (A2) is preferably 45 mol% or more, more preferably 70 mol% or more, still more preferably 90 mol% or more, and particularly preferably 99. More than mol%.
• the upper limit of the ratio is not particularly limited and is 100 mol% or less.
• the structural unit (A2) may include at least one type selected from the structural units (A21) to (A25), and is composed of only one type selected from the structural units (A21) to (A25). May be good.
• the structural unit (A2) contains two or more types of structural units selected from the structural units (A21) to (A25)
• the ratio of each structural unit in the structural unit (A2) is not particularly limited and is arbitrary. Can be.
• the ratio of the constituent unit (A2) in the constituent unit X2A is preferably 45 mol% or more, more preferably 60 mol% or more, still more preferably 85 mol% or more.
• the upper limit of the content ratio is not particularly limited and is 100 mol% or less.
• the structural unit X1A contains the structural unit (A1) and the structural unit X2A contains the structural unit (A2)
• the structural unit in the structural unit derived from the tetracarboxylic acid dianhydride of the imide-amidoic acid copolymer
• the molar ratio [(A1) / (A2)] of A1) to the constituent unit (A2) is preferably 10/90 to 55/45, more preferably 20/80 to 50/50, and even more preferably. Is 25/75 to 45/55.
• the structural unit Y1B is a structural unit derived from a diamine occupying the imide moiety (IM) and the amic acid moiety (AM1) of the copolymer of the present invention, and includes a structural unit (B1) derived from the diamine (b1).
• the structural unit (B1) is a structural unit (B11) derived from a compound represented by the following formula (b11), a structural unit (B12) derived from a compound represented by the following general formula (b12), and the following general formula. It contains at least one selected from the group consisting of the structural unit (B13) derived from the compound represented by (b13).
• the total ratio of the structural units (B11) to (B13) in the structural unit (B1) is preferably 45 mol% or more, more preferably 70 mol% or more, still more preferably 90 mol% or more, and particularly preferably 99. More than mol%.
• the upper limit of the ratio is not particularly limited and is 100 mol% or less.
• Z 1 represents a single bond or a group represented by —O—.
• R independently represents a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 5 carbon atoms.
• the structural unit (B11) is selected from the group consisting of the structural unit (B111) derived from the compound represented by the following formula (b111) and the structural unit (B112) derived from the compound represented by the following formula (b112). At least one is preferable.
• the structural unit (B11) may be only the structural unit (B111), may be only the structural unit (B112), or may be a combination of the structural unit (B111) and the structural unit (B112). .
• the compound represented by the formula (b111) is 4,4'-diaminodiphenylsulfone (4,4′-DDS), and the compound represented by the formula (b112) is 3,3′-diaminodiphenylsulfone (4,4′-DDS). 3,3'-DDS).
• the structural unit (B12) is selected from the group consisting of the structural unit (B121) derived from the compound represented by the following formula (b121) and the structural unit (B122) derived from the compound represented by the following formula (b122). It is preferable to include at least one structural unit (B122) derived from the compound represented by the following formula (b122) from the viewpoint of heat resistance, low residual stress and low coefficient of linear thermal expansion. More preferred.
• the compound represented by the formula (b121) is 2,2'-bis (trifluoromethyl) -4,4'-diaminodiphenyl ether (6FODA).
• the compound represented by the formula (b122) is 2,2'-bis (trifluoromethyl) benzidine (TFMB).
• the structural unit (B13) is a structural unit derived from the compound represented by the above formula (b13).
• R is independently a hydrogen atom, a fluorine atom or an alkyl group having 1 to 5 carbon atoms, and is preferably independently a hydrogen atom, a fluorine atom or a methyl group. More preferably, it is a hydrogen atom.
• Examples of the compound represented by the formula (b13) include 9,9-bis (4-aminophenyl) fluorene (BAFL), 9,9-bis (3-fluoro-4-aminophenyl) fluorene, and 9,9.
• -Bis (3-methyl-4-aminophenyl) fluorene and the like can be mentioned, and at least one selected from the group consisting of these three compounds is preferable, and 9,9-bis (4-amino) from the viewpoint of heat resistance. Phenyl) fluorene is more preferred.
• the structural unit Y1B may include a structural unit other than the structural unit (B1).
• the diamine giving such a constituent unit is not particularly limited, but is limited to 1,4-phenylenediamine, p-xylylene diamine, 3,5-diaminobenzoic acid, 1,5-diaminonaphthalene, and 2,2'-dimethyl.
• Examples thereof include aliphatic diamines such as diamines.
• the aromatic diamine means a diamine containing one or more aromatic rings
• the alicyclic diamine means a diamine containing one or more alicyclic rings and not containing an aromatic ring, and is a fat.
• the group diamine means a diamine that does not contain an aromatic ring or an alicyclic ring.
• the structural unit arbitrarily included in the structural unit Y1B may be one type or two or more types.
• the structural unit Y2B is a structural unit derived from a diamine occupying the amic acid portion (AM2) of the copolymer of the present invention, and the structural unit Y2B is from the viewpoints of low residual stress, low coefficient of linear thermal expansion, and heat resistance.
• Z 2 and Z 3 independently represent a group represented by -COO- or a group represented by -OCO-.
• R 1 , R 2 and R 3 are independent of each other. Then, it represents a monovalent organic group having 1 to 20 carbon atoms.
• H, i, j, and k are integers of 0 to 4.
• the structural unit (B2) preferably includes a structural unit (B21) derived from a compound represented by the following formula (b21) from the viewpoint of heat resistance, low residual stress and low coefficient of linear thermal expansion.
• the compound represented by the formula (b21) is 4-aminophenyl-4-aminobenzoate (4-BAAB).
• the structural unit Y2B may include a structural unit other than the structural unit (B2).
• the diamine giving such a constituent unit is not particularly limited, but is limited to 1,4-phenylenediamine, p-xylylene diamine, 3,5-diaminobenzoic acid, 1,5-diaminonaphthalene, and 2,2'-dimethyl.
• Alicyclic diamines such as methyl) cyclohexane; and aliphatic diamines such as ethylenediamine and hexamethylenediamine can be mentioned.
• the structural unit arbitrarily included in the structural unit Y2B may be one type or two or more types.
• the ratio of the structural unit (B1) in the structural unit derived from the diamine of the copolymer is preferably 10 to 55 mol%, more preferably 20. It is ⁇ 50 mol%, more preferably 25-45 mol%, still more preferably 35-45 mol%.
• the ratio of the structural unit (B2) in the structural unit derived from the diamine of the copolymer is preferably 45 to 90 mol%, more preferably 50. It is -80 mol%, more preferably 55-75 mol%, still more preferably 55-65 mol%.
• the constituent unit Y1B contains the constituent unit (B1) and the constituent unit Y2B contains the constituent unit (B2)
• the constituent unit (B1) and the constituent unit in the constituent unit derived from the diamine of the imide-amidoic acid copolymer is preferably 10/90 to 55/45, more preferably 20/80 to 50/50, and even more preferably 25/75 to 25/75. It is 45/55, and even more preferably 35/65 to 45/55.
• the total ratio of the structural unit (B1) and the structural unit (B2) in the structural unit derived from the diamine of the copolymer is preferably 70 mol. % Or more, more preferably 80 mol% or more, still more preferably 90 mol% or more, and the upper limit value is not particularly limited and is 100 mol% or less.
• the ratio of the total of the structural unit X1A, the structural unit X2A, the structural unit Y1B and the structural unit Y2B to the total of the structural units constituting the imide-amide acid copolymer is preferably 80% by mass or more, more preferably 82% by mass. As described above, it is more preferably 85% by mass or more, and the upper limit is not limited and is 100% by mass or less.
• the imide-amidoic acid copolymer of the present invention may contain a structural unit other than the above-mentioned structural unit X1A, structural unit X2A, structural unit Y1B and structural unit Y2B.
• the imide-amidoic acid copolymer of the present invention may further contain a structural unit (B3) derived from a compound represented by the following general formula (b3). Residual stress is reduced by including the structural unit (B3).
• Z 4 and Z 5 independently represent a divalent aliphatic group or a divalent aromatic group
• R 4 and R 5 independently represent a monovalent aromatic group or 1 respectively.
• R 6 and R 7 each independently represent a monovalent aliphatic group
• R 8 and R 9 each independently indicate a monovalent aliphatic group or a monovalent aromatic group.
• M and n each independently indicate an integer of 1 or more
• the sum of m and n indicates an integer of 2 to 1000.
• at least one of R 4 and R 5 shows a monovalent aromatic group.
• two or more different repeating units described in parallel by [] may be repeated in any form and order of random, alternating, or block, respectively.
• the divalent aliphatic group or divalent aromatic group in Z 4 and Z 5 may be substituted with a fluorine atom or may contain an oxygen atom.
• the carbon number shown below means all the carbon numbers contained in the aliphatic group or the aromatic group.
• the divalent aliphatic group include a divalent saturated or unsaturated aliphatic group having 1 to 20 carbon atoms.
• the divalent aliphatic group preferably has 3 to 20 carbon atoms.
• Examples of the divalent saturated aliphatic group include an alkylene group having 1 to 20 carbon atoms and an alkyleneoxy group, and examples of the alkylene group include a methylene group, an ethylene group, a propylene group, a trimethylene group, a tetramethylene group and a hexa.
• Methylene group, octamethylene group, decamethylene group, dodecamethylene group and the like can be exemplified, and examples of the alkyleneoxy group include propyleneoxy group and trimethyleneoxy group.
• Examples of the divalent unsaturated aliphatic group include an alkenylene group having 2 to 20 carbon atoms, and examples thereof include a vinylene group, a propenylene group, and an alkylene group having an unsaturated double bond at the terminal.
• Examples of the divalent aromatic group include an arylene group having 6 to 20 carbon atoms and an aralkylene group having 7 to 20 carbon atoms.
• Specific examples of the arylene group having 6 to 20 carbon atoms in Z 4 and Z 5 include an o-phenylene group, an m-phenylene group, a p-phenylene group, a 4,4′-biphenylylene group, a 2,6-naphthylene group and the like. Can be mentioned.
• As Z 4 and Z 5 a trimethylene group and a p-phenylene group are particularly preferable, and a trimethylene group is more preferable.
• the monovalent aliphatic group in R 4 to R 9 includes a monovalent saturated or unsaturated aliphatic group.
• the monovalent saturated aliphatic group include an alkyl group having 1 to 22 carbon atoms, and examples thereof include a methyl group, an ethyl group, and a propyl group.
• the monovalent unsaturated aliphatic group include an alkenyl group having 2 to 22 carbon atoms, and examples thereof include a vinyl group and a propenyl group. These groups may be substituted with fluorine atoms.
• the monovalent aromatic group in R 4 , R 5 , R 8 and R 9 of the formula (b3) was an aryl group having 6 to 20 carbon atoms, 7 to 30 carbon atoms, and was substituted with an alkyl group. Examples thereof include an aryl group and an aralkyl group having 7 to 30 carbon atoms. As the monovalent aromatic group, an aryl group is preferable, and a phenyl group is more preferable. At least one of R 4 and R 5 shows a monovalent aromatic group, but it is preferable that both R 4 and R 5 are monovalent aromatic groups, and both R 4 and R 5 are phenyl groups. Is more preferable.
• R 6 and R 7 an alkyl group having 1 to 6 carbon atoms is preferable, and a methyl group is more preferable.
• R 8 and R 9 a monovalent aliphatic group is preferable, and a methyl group is more preferable.
• the compound represented by the following formula (b31) is preferable.
• n and n are synonymous with m and n in the formula (b3), respectively, and the preferable range is also the same.
• m indicates the number of repetitions of the siloxane unit to which at least one monovalent aromatic group is bonded
• n in the formulas (b3) and (b31) is a monovalent aliphatic group. Indicates the number of repetitions of the siloxane unit to which is bonded.
• M and n in the formulas (b3) and (b31) independently represent integers of 1 or more, and the sum of m and n (m + n) represents an integer of 2 to 1000.
• the sum of m and n preferably represents an integer of 3 to 500, more preferably 3 to 100, and even more preferably an integer of 3 to 50.
• the ratio of m / n in the formulas (b3) and (b31) is preferably 5/95 to 50/50, more preferably 10/90 to 40/60, and even more preferably 20/80 to 30/70. ..
• the functional group equivalent (amine equivalent) of the compound represented by the formula (b3) is preferably 150 to 5,000 g / mol, more preferably 400 to 4,000 g / mol, and further preferably 500 to 3,000 g / mol. Is.
• the functional group equivalent means the mass of the compound represented by the formula (b3) per mole of the functional group (amino group).
• the ratio of the constituent unit (B3) to the total amount of the constituent unit (B3), the constituent unit Y1B and the constituent unit Y2B is preferably 0.01 to 15.0 mol%, more preferably. It is 0.5 to 12.0 mol%, more preferably 1.0 to 8.0 mol%.
• the content of the polyorganosiloxane unit with respect to the total of the structural units constituting the imide-amidoic acid copolymer is preferably 1 to 20% by mass, more preferably 2 to 18% by mass. More preferably, it is 5 to 15% by mass.
• the content of the polyorganosiloxane unit is within the above range, low retardation and low residual stress can be achieved at a higher level.
• Examples of commercially available compounds represented by the formula (b3) include “X-22-9409” and “X-22-1660B-3” manufactured by Shin-Etsu Chemical Co., Ltd.
• the imide-amidoic acid copolymer of the present invention may be produced by any method, but it is preferably obtained by the following method.
• the method for producing an imide-amidoic acid copolymer of the present invention includes the following steps 1 and 2. Step 1: The tetracarboxylic acid component constituting the imide moiety (IM) is reacted with the diamine component to obtain an imide oligomer. Step 2: The imide oligomer obtained in Step 1 and the amic acid moiety (AM2) are formed.
• tetracarboxylic acid component and the diamine component are reacted to form an imide containing a repeating unit represented by the following formula (1), which is composed of an imide moiety (IM), an amide moiety (AM1) and an amic acid moiety (AM2).
• IM imide moiety
• AM1 amide moiety
• AM2 amic acid moiety
• X 1 is a tetravalent alicyclic group having 4 to 39 carbon atoms, and the bonding groups are -O-, -SO 2- , -CO-, -CH 2- , -C (CH 3 ) 2 -,-. It may have at least one selected from the group consisting of C 2 H 4 O- and -S-.
• X 2 is a tetravalent aromatic group having 4 to 39 carbon atoms, and has -O-, -SO 2- , -CO-, -CH 2- , -C (CH 3 ) 2 -,-as a bonding group. It may have at least one selected from the group consisting of C 2 H 4 O- and -S-.
• Y 1 is a group represented by at least one selected from the group consisting of the following formula (2), the following general formula (3), and the following general formula (4).
• Y 2 is a group represented by the following general formula (5). s, t and u are positive integers. ) (In formula (3), Z 1 represents a single bond or a group represented by —O—.
• R independently represents a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 5 carbon atoms.
• Z 2 and Z 3 independently represent a group represented by -COO- or a group represented by -OCO-.
• R 1 , R 2 and R 3 are independent of each other. Then, it represents a monovalent organic group having 1 to 20 carbon atoms.
• H, i, j, and k are integers of 0 to 4).
• the imide moiety and the amic acid moiety can be controlled to a specific structure, so that the conventional imide moiety and the amic acid moiety are randomly present.
• the imide-amide acid is expected to improve heat resistance and low residual stress because it has a polyimide portion and a polyamic acid portion according to the thermal imidization reactivity of each component. It is considered that a copolymer can be obtained.
• the preferred method for producing a copolymer of the present invention includes the following steps 1 and 2.
• Step 1 A compound that gives the structural unit X1A derived from tetracarboxylic acid dianhydride and a compound that gives the structural unit Y1B derived from diamine are reacted to obtain an imide oligomer.
• Step 2 The imide obtained in step 1. The oligomer is reacted with a compound that gives the structural unit X2A derived from tetracarboxylic acid dianhydride and a compound that gives the structural unit Y2B derived from diamine, and the imide moiety (IM) represented by the above formula (1) and the amide are reacted.
• IM imide moiety
• the compound giving the constituent unit X1A is an alicyclic tetracarboxylic acid dianhydride.
• the compound giving the building block X2A comprises an aromatic tetracarboxylic dianhydride and contains.
• the compound that gives the structural unit Y1B includes the compound that gives the structural unit (B1), and the compound that gives the structural unit (B1) is a compound represented by the following formula (b11) and represented by the following general formula (b12). It comprises at least one selected from the group consisting of a compound and a compound represented by the following general formula (b13).
• the compound giving the structural unit Y2B includes a compound represented by the following general formula (b2).
• Z 1 represents a single bond or a group represented by —O—.
• R independently represents a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 5 carbon atoms.
• Z 2 and Z 3 independently represent a group represented by -COO- or a group represented by -OCO-.
• R 1 , R 2 , and R 3 independently represent monovalent organic groups having 1 to 20 carbon atoms.
• h, i, j, and k are integers from 0 to 4.
• Step 1 is a step of reacting the tetracarboxylic acid component constituting the imide moiety (IM) with the diamine component to obtain an imide oligomer.
• the tetracarboxylic acid component constituting the imide moiety (IM) is preferably an alicyclic tetracarboxylic dianhydride.
• Step 1 is a step of reacting a compound giving a structural unit X1A derived from tetracarboxylic dianhydride with a compound giving a structural unit Y1B derived from a diamine to obtain an imide oligomer.
• the compound giving the building block X1A comprises an aromatic tetracarboxylic dianhydride.
• the compound giving the structural unit Y1B includes a compound giving the structural unit (B1), and the compound giving the structural unit (B1) is represented by the compound represented by the formula (b11) and the general formula (b12). It contains at least one selected from the group consisting of a compound and a compound represented by the general formula (b13).
• the tetracarboxylic acid component used in step 1 preferably contains a compound that gives a constituent unit (A1), and it is preferable that the entire amount thereof is used in step 1, as long as the effect of the present invention is not impaired. It may contain a tetracarboxylic acid component other than the compound giving (A1).
• the diamine component used in step 1 preferably contains a compound that gives the constituent unit (B1), and contains a diamine component other than the compound that gives the constituent unit (B1) as long as the effect of the present invention is not impaired. May be good.
• the diamine component with respect to the tetracarboxylic acid component is preferably 1.01 to 2 mol, more preferably 1.05 to 1.9 mol, and 1.1 to 1.7 mol. Is even more preferable.
• the method for reacting the tetracarboxylic acid component with the diamine component for obtaining the imide oligomer in step 1 is not particularly limited, and a known method can be used.
• Specific reaction methods include (1) charging a tetracarboxylic acid component, a diamine component, and a reaction solvent into a reactor, stirring at 10 to 110 ° C. for 0.5 to 30 hours, and then raising the temperature to imidize. Method of carrying out the reaction, (2) After charging the diamine component and the reaction solvent into the reactor and dissolving them, the tetracarboxylic acid component is charged, and if necessary, the mixture is stirred at 10 to 110 ° C. for 0.5 to 30 hours, and then.
• Examples thereof include a method of carrying out an imidization reaction by raising the temperature to (3) a method of charging a tetracarboxylic acid component, a diamine component and a reaction solvent into a reactor and immediately raising the temperature to carry out the imidization reaction.
• the imidization reaction it is preferable to carry out the reaction while removing water generated during production using a Dean-Stark apparatus or the like. By performing such an operation, the degree of polymerization and the imidization rate can be further increased.
• a known imidization catalyst can be used.
• the imidization catalyst include a base catalyst and an acid catalyst.
• Base catalysts include pyridine, quinoline, isoquinoline, ⁇ -picoline, ⁇ -picoline, 2,4-lutidine, 2,6-lutidine, trimethylamine, triethylamine, tripropylamine, tributylamine, triethylenediamine, imidazole, N, N.
• Examples thereof include organic base catalysts such as dimethylaniline and N, N-diethylaniline, and inorganic base catalysts such as potassium hydroxide, sodium hydroxide, potassium carbonate, sodium carbonate, potassium hydrogencarbonate and sodium hydrogencarbonate.
• the acid catalyst examples include crotonic acid, acrylic acid, trans-3-hexenoic acid, cinnamic acid, benzoic acid, methylbenzoic acid, oxybenzoic acid, terephthalic acid, benzenesulfonic acid, paratoluenesulfonic acid, naphthalenesulfonic acid and the like. Can be mentioned.
• the above-mentioned imidization catalyst may be used alone or in combination of two or more.
• a base catalyst is preferable, an organic base catalyst is more preferable, one or more selected from triethylamine and triethylenediamine is more preferable, and triethylamine is even more preferable.
• the temperature of the imidization reaction is preferably 120 to 250 ° C., more preferably 160 to 200 ° C. from the viewpoint of suppressing the reaction rate and gelation.
• the reaction time is preferably 0.5 to 10 hours after the start of distillation of the produced water.
• the imide oligomer obtained in step 1 preferably has an imide repeating structural unit formed from a compound giving a structural unit (A1) and a compound giving a structural unit (B1). Further, the oligomer obtained in step 1 preferably has amino groups at both ends of the main chain of the molecular chain.
• a solution containing an imide oligomer dissolved in a solvent can be obtained.
• the solution containing the imide oligomer obtained in step 1 contains at least a part of the components used as the tetracarboxylic acid component and the diamine component in step 1 as unreacted monomers as long as the effects of the present invention are not impaired. You may.
• step 2 in the production method of the present invention the imide oligomer obtained in step 1 is reacted with the tetracarboxylic acid component and the diamine component constituting the amic acid moiety (AM2), and is represented by the above formula (1).
• This is a step of obtaining an imide-amide acid copolymer containing a repeating unit consisting of an imide moiety (IM), an amic acid moiety (AM1) and an amic acid moiety (AM2).
• the tetracarboxylic acid component constituting the amic acid moiety (AM2) used in step 2 is preferably an aromatic tetracarboxylic dianhydride.
• Step 2 is a step of reacting a compound that gives the structural unit X2A derived from tetracarboxylic acid dianhydride and a compound that gives the structural unit Y2B derived from diamine to obtain an imide-amide acid copolymer.
• the compound giving the building block X2A comprises an aromatic tetracarboxylic dianhydride.
• the compound giving the structural unit Y2B includes a compound giving the structural unit (B2), and the compound giving the structural unit (B2) includes the compound represented by the general formula (b2), which is represented by the above formula (b21). It is preferable to contain the compound to be used.
• the tetracarboxylic acid component used in step 2 preferably contains a compound that gives the constituent unit (A2), and is a tetracarboxylic acid component other than the compound that gives the constituent unit (A2) as long as the effect of the present invention is not impaired. May include.
• Examples of the tetracarboxylic acid component other than the compound giving the structural unit (A2) include a compound giving the structural unit (A1), except that the tetracarboxylic acid component used in step 2 gives the structural unit (A1). It is preferable that it does not contain a compound. Further, it is preferable that the entire amount of the compound giving the structural unit (A2) is used in the step 2.
• the diamine component used in step 2 preferably contains a compound that gives the constituent unit (B2), and contains a diamine component other than the compound that gives the constituent unit (B2) as long as the effect of the present invention is not impaired. May be good.
• a diamine or tetracarboxylic acid dianhydride containing the polyorganosiloxane unit may be reacted, and the polyorganosiloxane unit may be used. It is preferable to react the contained diamine, and it is more preferable to react the compound giving the constituent unit (B3).
• the method for reacting the tetracarboxylic acid component with the imide oligomer obtained in step 1 for obtaining the imide-amide acid copolymer in step 2 is not particularly limited, and a known method can be used.
• a specific reaction method (1) the imide oligomer, the tetracarboxylic acid component, the diamine component and the solvent obtained in step 1 are charged into the reactor, and 1 in the range of 0 to 120 ° C., preferably 5 to 80 ° C.
• a copolymer solution containing an imide-amidoic acid copolymer dissolved in a solvent can be obtained.
• the concentration of the copolymer in the obtained copolymer solution is usually 1 to 50% by mass, preferably 3 to 35% by mass, and more preferably 5 to 30% by mass.
• the number average molecular weight of the imide-amidoic acid copolymer obtained by the production method of the present invention is preferably 5,000 to 500,000 from the viewpoint of the mechanical strength of the obtained polyimide film.
• the weight average molecular weight (Mw) is preferably 10,000 to 800,000, more preferably 100,000 to 300,000.
• the number average molecular weight of the copolymer can be determined from, for example, a standard polymethylmethacrylate (PMMA) conversion value measured by gel filtration chromatography. Next, the raw materials and the like used in this production method will be described.
• ⁇ Tetracarboxylic acid component> The tetracarboxylic acid component used as a raw material for the imide-amide acid copolymer in the present production method is described in (Constituent Unit XIA) and (Constituent Unit X2A) of the above ⁇ Constituent Units of Imid-Amidic Acid Copolymer>. It is preferable to use a compound that gives each constituent unit.
• the compound giving the structural unit (A1) includes, but is not limited to, a compound represented by the formula (a11), a compound represented by the formula (a12), and a compound represented by the formula (a13). , It may be a derivative thereof as long as it gives the same structural unit.
• Examples of the derivative include a tetracarboxylic acid corresponding to the compound represented by any of the formulas (a11) to (a13) and an alkyl ester of the tetracarboxylic acid.
• the compound that gives the structural unit (A1) the compound represented by any of the formulas (a11) to (a13) is preferable.
• the compound represented by the formula (a2) the compound represented by the formula (a21), the compound represented by the formula (a22), the compound represented by the formula (a23), and the compound represented by the formula (a24) are represented.
• Examples thereof include the compound to be used and the compound represented by the formula (a25), but the present invention is not limited to the above, and a derivative thereof may be used as long as the same structural unit is given.
• Examples of the derivative include a tetracarboxylic acid corresponding to the compound represented by any of the formulas (a21) to (a25) and an alkyl ester of the tetracarboxylic acid.
• the compound giving the structural unit (A2) the compound represented by any of the formulas (a21) to (a25) is preferable.
• the molar ratio of the compound giving the structural unit (A1) to the compound giving the structural unit (A2) in the tetracarboxylic acid component used as the raw material of the imide-amidoic acid copolymer in this production method [(A1) / ( A2)] is preferably 10/90 to 55/45, more preferably 20/80 to 50/50, and even more preferably 25/75 to 45/55.
• the total ratio of the compounds giving the structural units (A11) to (A13) to the compounds giving the structural unit (A1) is preferably 45 mol% or more, more preferably 70 mol% or more, still more preferably 90 mol%. As mentioned above, it is particularly preferably 99 mol% or more.
• the upper limit of the ratio is not particularly limited and is 100 mol% or less.
• the total ratio of the compounds giving the constituent units (A21) to (A25) to the compounds giving the constituent unit (A2) is preferably 45 mol% or more, more preferably 70 mol% or more, still more preferably 90. It is mol% or more, particularly preferably 99 mol% or more.
• the upper limit of the ratio is not particularly limited and is 100 mol% or less.
• the tetracarboxylic acid component used as a raw material for the imide-amidic acid copolymer includes a compound that gives a constituent unit (A1), a compound that gives a constituent unit (A21), a compound that gives a constituent unit (A22), and a constituent unit (A23). ),
• the compound giving the structural unit (A24), and the compound other than the compound giving the structural unit (A25) may be included, and the compound may be one kind or two or more kinds.
• ⁇ Diamine component> The molar ratio of the compound giving the structural unit (B1) to the compound giving the structural unit (B2) in the diamine component used as the raw material of the imide-amidoic acid copolymer in this production method [(B1) / (B2)). ] Is preferably 10/90 to 55/45, more preferably 20/80 to 50/50, still more preferably 25/75 to 45/55, and even more preferably 35/65 to 45. / 55.
• the compound that gives the structural unit (B1) one or more selected from the group consisting of a compound that gives the structural unit (B11), a compound that gives the structural unit (B12), and a compound that gives the structural unit (B13) is preferable.
• the total ratio of the compounds giving the structural units (B11) to (B13) to the compounds giving the structural unit (B1) is preferably 45 mol% or more, more preferably 70 mol% or more, still more preferably 90 mol%. As mentioned above, it is particularly preferably 99 mol% or more. The upper limit of the ratio is not particularly limited and is 100 mol% or less.
• the compound that gives the structural unit (B2) one or more compounds that give the structural unit (B2) are preferable.
• the diamine component used as a raw material of the imide-amidoic acid copolymer is given a compound that gives a constituent unit (B11), a compound that gives a constituent unit (B12), a compound that gives a constituent unit (B13), and (B2).
• a compound other than the compound may be contained, and the compound may be one kind or two or more kinds.
• Examples of the compound giving the structural unit (B1) and the compound giving the structural unit (B2) include, but are not limited to, diamines, and may be derivatives thereof as long as the same structural unit is given. Examples of the derivative include diisocyanates corresponding to diamines.
• diamine is preferable as the compound that gives the structural unit (B1) and the compound that gives the structural unit (B2).
• the compound giving the constituent unit (B3) is preferably 0.01 with respect to the total amount of the compound giving the constituent unit (B3) and the diamine component. It contains from 15.0 mol%, more preferably 0.5 to 12.0 mol%, still more preferably 1.0 to 8.0 mol%.
• the tetracarboxylic acid component used in all steps of the production of the copolymer including the reaction step with other components such as a compound giving the constituent unit (B3) after the completion of steps 1, 2 and 2 The ratio of the amount of the diamine component charged is preferably 0.9 to 1.1 mol of the diamine component with respect to 1 mol of the tetracarboxylic acid component.
• an end-capping agent may be used for producing the imide-amidoic acid copolymer.
• the terminal encapsulant is preferably used in the reaction step with other components such as a compound that gives the structural unit (B3) in step 2 or after the completion of step 2.
• monoamines or dicarboxylic acids are preferable.
• the amount of the end-capping agent to be introduced is preferably 0.0001 to 0.1 mol, particularly preferably 0.001 to 0.06 mol, based on 1 mol of the tetracarboxylic acid component.
• Examples of monoamine terminal sealants include methylamine, ethylamine, propylamine, butylamine, benzylamine, 4-methylbenzylamine, 4-ethylbenzylamine, 4-dodecylbenzylamine, 3-methylbenzylamine, 3-. Ethylbenzylamine, aniline, 3-methylaniline, 4-methylaniline and the like are recommended. Of these, benzylamine and aniline can be preferably used.
• dicarboxylic acid terminal encapsulant dicarboxylic acids are preferable, and a part thereof may be ring-closed.
• phthalic acid, phthalic anhydride, 4-chlorophthalic acid, tetrafluorophthalic acid, 2,3-benzophenonedicarboxylic acid, 3,4-benzophenonedicarboxylic acid, cyclopentane-1,2-dicarboxylic acid, 4-cyclohexene-1. , 2-Dicarboxylic acid, etc. are recommended.
• phthalic acid and phthalic anhydride can be preferably used.
• the solvent used in the method for producing the copolymer of the present invention may be any as long as it can dissolve the produced imide-amidoic acid copolymer.
• an aprotic solvent, a phenol solvent, an ether solvent, a carbonate solvent and the like can be mentioned.
• aprotonic solvent examples include N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam, 1,3-dimethylimidazolidinone, tetramethylurea and the like.
• Amide-based solvents lactone-based solvents such as ⁇ -butyrolactone and ⁇ -valerolactone, phosphorus-containing amide-based solvents such as hexamethylphosphoric amide and hexamethylphosphintriamide, and sulfur-containing solvents such as dimethylsulfone, dimethylsulfoxide, and sulfolane.
• Examples thereof include a system solvent, a ketone solvent such as acetone, methyl ethyl ketone, cyclohexanone and methylcyclohexanone, and an ester solvent such as acetic acid (2-methoxy-1-methylethyl).
• a system solvent such as acetone, methyl ethyl ketone, cyclohexanone and methylcyclohexanone
• an ester solvent such as acetic acid (2-methoxy-1-methylethyl).
• phenolic solvent examples include phenol, o-cresol, m-cresol, p-cresol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4. -Xylenol, 3,5-xylenol and the like can be mentioned.
• ether solvent examples include 1,2-dimethoxyethane, bis (2-methoxyethyl) ether, 1,2-bis (2-methoxyethoxy) ethane, and bis [2- (2-methoxyethoxy) ethyl]. Examples include ether, tetrahydrofuran, 1,4-dioxane and the like.
• the carbonate solvent examples include diethyl carbonate, methyl ethyl carbonate, ethylene carbonate, propylene carbonate and the like.
• an amide solvent or a lactone solvent is preferable, an amide solvent is more preferable, and N-methyl-2-pyrrolidone is further preferable.
• the above reaction solvent may be used alone or in combination of two or more.
• the varnish of the present invention is obtained by dissolving the imide-amidoic acid copolymer of the present invention, which is a precursor of a polyimide resin, in an organic solvent. That is, the varnish of the present invention contains the copolymer of the present invention and an organic solvent, and the copolymer is dissolved in the organic solvent.
• the organic solvent is not particularly limited as long as it dissolves the copolymer of the present invention, but the above-mentioned compounds are used alone or in combination of two or more as the solvent used for producing the copolymer of the present invention. It is preferable to use it.
• the varnish of the present invention may be the above-mentioned copolymer solution itself, or may be obtained by further adding a diluting solvent to the copolymer solution.
• the varnish of the present invention may further contain an imidization catalyst and a dehydration catalyst from the viewpoint of efficiently advancing the imidization of the amic acid moiety in the copolymer of the present invention.
• the imidization catalyst may be any imidization catalyst having a boiling point of 40 ° C. or higher and 180 ° C. or lower, and an amine compound having a boiling point of 180 ° C. or lower is preferable. If the imidization catalyst has a boiling point of 180 ° C. or lower, the film is not colored when dried at a high temperature after the film is formed, and the appearance is not impaired. Further, if the imidization catalyst has a boiling point of 40 ° C. or higher, the possibility of volatilization before the imidization proceeds sufficiently can be avoided.
• Examples of the amine compound preferably used as an imidization catalyst include pyridine and picoline.
• the above-mentioned imidization catalyst may be used alone or in combination of two or more.
• Examples of the dehydration catalyst include acid anhydrides such as acetic anhydride, propionic acid anhydride, n-butyric acid anhydride, benzoic acid anhydride, and trifluoroacetic anhydride; and carbodiimide compounds such as dicyclohexylcarbodiimide. These may be used alone or in combination of two or more.
• the varnish of the present invention preferably contains the copolymer of the present invention in an amount of 3 to 40% by mass, more preferably 5 to 40% by mass, and even more preferably 10 to 30% by mass.
• the viscosity of the varnish is preferably 0.1 to 100 Pa ⁇ s, more preferably 0.1 to 20 Pa ⁇ s.
• the viscosity of the varnish is a value measured at 25 ° C. using an E-type viscometer.
• the varnish of the present invention has an inorganic filler, an adhesion accelerator, a release agent, a flame retardant, an ultraviolet stabilizer, a surfactant, a leveling agent, an antifoaming agent, and an optical brightener as long as the required properties of the polyimide film are not impaired.
• Various additives such as an agent, a cross-linking agent, a polymerization initiator, and a photosensitizer may be contained.
• the method for producing the varnish of the present invention is not particularly limited, and a known method can be applied.
• the polyimide film of the present invention contains a polyimide resin obtained by imidizing the amic acid moiety in the imide-amidoic acid copolymer of the present invention. Therefore, the polyimide film of the present invention is excellent in transparency and heat resistance, has a low yellowness, and exhibits low residual stress. Suitable physical property values of the polyimide film of the present invention are as described above.
• the polyimide film of the present invention can be produced by using a varnish in which the above-mentioned copolymer is dissolved in an organic solvent.
• the method for producing a polyimide film using the varnish of the present invention is not particularly limited, and a known method can be used.
• the varnish of the present invention is applied or formed into a film on a smooth support such as a glass plate, a metal plate, or a plastic, and then an organic solvent such as a reaction solvent or a diluting solvent contained in the varnish is heated.
• a polyimide film is produced by removing it to obtain a copolymer film, imidizing (dehydrating and ring-closing) the amic acid moiety of the copolymer in the copolymer film by heating, and then peeling it from the support. be able to.
• the weight average molecular weight (Mw) of the polyimide resin contained in the polyimide film of the present invention is preferably 10,000 to 800,000, more preferably 30,000 to 500,000, from the viewpoint of the mechanical strength of the film. It is even more preferably 50,000 to 400,000, and even more preferably 100,000 to 300,000.
• the number average molecular weight of the copolymer can be determined from, for example, a standard polymethylmethacrylate (PMMA) conversion value measured by gel filtration chromatography.
• the heating temperature for drying the varnish of the present invention to obtain a copolymer film is preferably 50 to 150 ° C.
• the heating temperature for imidizing the copolymer of the present invention by heating is preferably 200 to 500 ° C, more preferably 250 to 450 ° C, and even more preferably 300 to 400 ° C.
• the heating time is usually 1 minute to 6 hours, preferably 5 minutes to 2 hours, and more preferably 15 minutes to 1 hour.
• Examples of the heating atmosphere include air gas, nitrogen gas, oxygen gas, hydrogen gas, and nitrogen / hydrogen mixed gas.
• nitrogen gas and hydrogen concentration having an oxygen concentration of 100 ppm or less are used.
• a nitrogen / hydrogen mixed gas containing 0.5% or less is preferable.
• the imidization method is not limited to thermal imidization, and chemical imidization can also be applied.
• the thickness of the polyimide film of the present invention can be appropriately selected depending on the intended use, but is preferably 1 to 250 ⁇ m, more preferably 5 to 100 ⁇ m, and even more preferably 5 to 50 ⁇ m. When the thickness is 1 to 250 ⁇ m, it can be practically used as a self-supporting film. The thickness of the polyimide film can be easily controlled by adjusting the solid content concentration and viscosity of the varnish.
• the total light transmittance is preferably 85% or more, more preferably 86% or more, still more preferably 87% or more when the film has a thickness of 10 ⁇ m.
• the yellow index (YI) is preferably 15.0 or less, more preferably 13.0 or less, still more preferably 12.0 or less, still more preferably 11.0 or less when the film has a thickness of 10 ⁇ 3 ⁇ m. Is.
• the glass transition temperature (Tg) is preferably 350 ° C.
• the above-mentioned physical property values in the present invention can be specifically measured by the method described in Examples.
• the polyimide film of the present invention is suitably used as a film for various members such as color filters, flexible displays, semiconductor parts, and optical members.
• the polyimide film of the present invention is particularly preferably used as a substrate for an image display device such as a liquid crystal display or an OLED display.
• CTE Coefficient of linear thermal expansion
• Td1% 1% weight loss temperature (Td1%)
• TG / DTA6200 a differential thermogravimetric simultaneous measurement device manufactured by Hitachi High-Tech Science Corporation was used. The temperature of the sample was raised to 40 to 550 ° C. at a heating rate of 10 ° C./min, and the temperature at which the weight was reduced by 1% as compared with the weight at 300 ° C. was defined as the 1% weight loss temperature. The larger the value, the better the weight loss temperature.
• Tensile strength and tensile elastic modulus The tensile strength and tensile elastic modulus were measured using a tensile tester "Strograph VG-1E" manufactured by Toyo Seiki Co., Ltd. in accordance with JIS K7127: 1999. The distance between the chucks was 50 mm, the size of the test piece was 10 mm ⁇ 70 mm, and the test speed was 20 mm / min.
• Residual stress Example using a residual stress measuring device "FLX-2320" manufactured by KLA Tencor Co., Ltd., on a 4-inch silicon wafer having a thickness of 525 ⁇ m ⁇ 25 ⁇ m for which the “warp amount” has been measured in advance.
• the varnish obtained in the comparative example was applied using a spin coater and prebaked.
• heat curing treatment was performed at 400 ° C. for 60 minutes (heating rate 5 ° C./min) in a nitrogen atmosphere to prepare a silicon wafer with a polyimide film having a thickness of 6 to 15 ⁇ m after curing. bottom.
• the amount of warpage of this wafer was measured using the above-mentioned residual stress measuring device, and the residual stress generated between the silicon wafer and the polyimide film was evaluated.
• TFMB 2,2'-bis (trifluor
• Example 1 9.932 g of 4,4'-DDS in a 500 mL five-necked round-bottom flask equipped with a stainless half-moon agitator, a nitrogen inlet tube, a Dean Stark with a cooling tube, a thermometer, and a glass end cap. 0.040 mol) and 44.603 g of NMP were added, and the mixture was stirred at a system temperature of 70 ° C. and a nitrogen atmosphere at a rotation speed of 200 rpm to obtain a solution.
• Example 2 The amount of CpODA was changed from 11.531 (0.030 mol) to 7.688 g (0.020 mol), and the amount of s-BPDA was changed from 20.595 g (0.070 mol) to 23.538 g (0.080 mol). The amount of 4,4'-DDS was changed from 9.932 (0.040 mol) to 7.449 g (0.030 mol), and the amount of 4-BAAB was 13.695 (0.
• a varnish having a solid content concentration of about 15% by mass was obtained by the same method as in Example 1 except that the amount was changed from 060 mol) to 15.978 g (0.070 mol). Using the obtained varnish, a film was obtained by the same method as in Example 1.
• Example 3 Polyimide having a solid content concentration of about 15% by mass by the same method as in Example 1 except that 9,932 g (0.040 mol) of 4,4'-DDS was changed to 12.810 g (0.040 mol) of TFMB. I got a varnish. Using the obtained varnish, a film was obtained by the same method as in Example 1.
• Example 4 The amount of CpODA was changed from 11.531 (0.030 mol) to 7.688 g (0.020 mol), and the amount of s-BPDA was changed from 20.595 g (0.070 mol) to 23.538 g (0.080 mol).
• the amount of TFMB was changed from 12.810 (0.040 mol) to 9.607 g (0.030 mol), and the amount of 4-BAAB was changed from 13.695 (0.060 mol) to 15.
• a varnish having a solid content concentration of about 15% by mass was obtained by the same method as in Example 3 except that the amount was changed to .978 g (0.070 mol). Using the obtained varnish, a film was obtained by the same method as in Example 1.
• Example 5 Same as in Example 1 except that 9,932 g (0.040 mol) of 4,4'-DDS was changed to 6.405 g (0.020 mol) of TFMB and 6.969 g (0.020 mol) of BAFL. By the method, a varnish having a solid content concentration of about 15% by mass was obtained. Using the obtained varnish, a film was obtained by the same method as in Example 1.
• Example 6 The amount of CpODA was changed from 11.531 (0.030 mol) to 19.219 g (0.050 mol) and the amount of s-BPDA was changed from 20.595 g (0.070 mol) to 14.711 g (0.050 mol).
• the amount of TFMB was changed from 12.810 (0.040 mol) to 19.214 g (0.060 mol), and the amount of 4-BAAB was changed from 13.695 (0.060 mol) to 9
• a varnish having a solid content concentration of about 15% by mass was obtained by the same method as in Example 3 except that the amount was changed to .130 g (0.040 mol). Using the obtained varnish, a film was obtained by the same method as in Example 1.
• Example 1 The polyamic acid obtained in Comparative Example 1 has only an amic acid repeating structural unit formed from s-BPDA and 4-BAAB.
• Example 4 A varnish having a solid content concentration of about 15% by mass was obtained by the same method as in Example 3 except that 13.695 g (0.060 mol) of 4-BAAB was changed to 13.636 g (0.060 mol) of DABA. .. Using the obtained varnish, a film was obtained by the same method as in Example 1.
• the polyimide film obtained from the imide-amide acid copolymer of the example having a specific imide repeating structural unit and amic acid structural unit has low residual stress, excellent transparency, and low yellow color. It can be seen that the degree is excellent and the heat resistance is also excellent. Further comparing Example 1 and Comparative Example 3, the raw material composition constituting the polyimide is the same, but the polyimide film of Example 1 is excellent in low residual stress as compared with the polyimide film of Comparative Example 3 obtained from polyamic acid. It was a thing.

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