WO2021153379A1 - Résine polyimide, vernis polyimide et film polyimide - Google Patents

Résine polyimide, vernis polyimide et film polyimide Download PDF

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Publication number
WO2021153379A1
WO2021153379A1 PCT/JP2021/001883 JP2021001883W WO2021153379A1 WO 2021153379 A1 WO2021153379 A1 WO 2021153379A1 JP 2021001883 W JP2021001883 W JP 2021001883W WO 2021153379 A1 WO2021153379 A1 WO 2021153379A1
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structural unit
mol
polyimide
compound
compound represented
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PCT/JP2021/001883
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English (en)
Japanese (ja)
Inventor
洋平 安孫子
三田寺　淳
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三菱瓦斯化学株式会社
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Priority to CN202180011291.2A priority Critical patent/CN115038737A/zh
Priority to JP2021574671A priority patent/JPWO2021153379A1/ja
Priority to KR1020227024120A priority patent/KR20220134534A/ko
Publication of WO2021153379A1 publication Critical patent/WO2021153379A1/fr

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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
    • C08G73/1039—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors comprising halogen-containing substituents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • 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
    • 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 resin, a polyimide varnish and a polyimide film.
  • polyimide resin Since polyimide resin has excellent mechanical properties, various uses are being studied in fields such as electrical and electronic parts. 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, and a polyimide resin suitable as the plastic material is desired. Research is also underway. High transparency is also required for such applications.
  • Patent Document 1 states that norbornane-2-spiro- ⁇ -cyclopentanone- ⁇ '-spiro-2''-norbornane for the purpose of high transparency, bending resistance, high heat resistance, and low coefficient of linear thermal expansion.
  • -5,5'', 6,6''-Polyimides containing repeating units made from tetracarboxylic acids and having a coefficient of linear thermal expansion of 50 to 400 ° C. of 100 ppm / K or less and their precursors are disclosed. There is.
  • a polyimide film substrate When a polyimide film substrate is used as an image display device such as a liquid crystal display or an OLED display, the substrate is required to have heat resistance, especially in the step of forming a polysilicon film on the substrate. Further, in recent years, in order to realize thinning and flexibility of devices, polyimide films are also required to be stretched, which is one of the indicators of toughness. However, the film having excellent heat resistance was hard and had poor elongation. Further, in display applications, not only the above-mentioned transparency but also colorlessness is more important. As described above, there has been a demand for a polyimide resin capable of obtaining a polyimide film having both heat resistance and elongation and excellent colorless transparency. An object of the present invention is to provide a polyimide resin that has both heat resistance and elongation, and is also excellent in colorless transparency.
  • the present inventors have found that a polyimide resin containing a combination of specific structural units can solve the above-mentioned problems, and have completed the invention.
  • the structural unit A further includes the structural unit (A2), and the structural unit (A2) is represented by the structural unit (A21) derived from the compound represented by the following formula (a21) and the following formula (a22).
  • Polygonide resin which is at least one selected from the group consisting of the structural unit (A22) derived from the compound to be used and the structural unit (A23) derived from the compound represented by the following formula (a23).
  • the structural unit B further includes the structural unit (B2), and the structural unit (B2) is represented by the structural unit (B21) derived from the compound represented by the following formula (b21) and the following formula (b22).
  • the polyimide resin of the present invention has both heat resistance and elongation, and is also excellent in colorless transparency.
  • the polyimide resin of the present invention is a polyimide resin containing a structural unit A derived from tetracarboxylic acid dianhydride and a structural unit B derived from diamine, and the structural unit A is represented by the following formula (a1).
  • the polyimide resin of the present invention contains the structural units (A1) and (B1) to achieve both heat resistance and elongation and is also excellent in colorless transparency is not clear, but the norbornane skeleton, ether bond, etc. It is considered that this is a combined effect due to the rigidity and randomness of the molecular chain due to.
  • the structural unit A is a structural unit derived from tetracarboxylic dianhydride, and includes a structural unit (A1) derived from the compound represented by the formula (a1).
  • the structural unit (A1) improves heat resistance, elongation, and colorless transparency, and above all, heat resistance and colorless transparency are improved.
  • the compound represented by the formula (a1) is norbornane-2-spiro- ⁇ -cyclopentanone- ⁇ '-spiro-2''-norbornane-5,5'', 6,6''-tetracarboxylic dianhydride. It is an anhydride.
  • the structural unit A may include a structural unit other than the structural unit (A1).
  • the structural unit A preferably further includes the structural unit (A2) in addition to the structural unit (A1).
  • the structural unit (A2) is a structural unit derived from the compound represented by the following formula (a2). Depending on the structural unit (A2), the elongation is particularly improved, and the mechanical properties such as strength are also improved.
  • L is a single bond or divalent linking group.
  • the divalent linking group is preferably a substituted or unsubstituted alkylene group, more preferably -CR 1 R 2- (where R 1 and R 2 are independently hydrogen atoms or substituted or substituted or It is an unsubstituted alkyl group, or R 1 and R 2 are bonded to each other to form a ring).
  • L is preferably one selected from the group consisting of a single bond, a group represented by the following formula (L1) and a group represented by the following formula (L2).
  • * indicates a binding site with an aromatic ring.
  • 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).
  • ) Is preferably at least one selected from the group consisting of the structural unit (A23) derived from the compound represented by the following formula (a21), and the structural unit (A21) derived from the compound represented by the following formula (a21) and the following. It is preferable that it is at least one selected from the group consisting of the structural unit (A22) derived from the compound represented by the formula (a22), and from the viewpoint of improving the elongation, the compound represented by the following formula (a21) is selected.
  • the structural unit (A21) derived from the compound is more preferable, and the structural unit (A22) derived from the compound represented by the following formula (a22) is more preferable from the viewpoint of heat resistance. That is, it is more preferable that the structural unit A further includes the structural unit (A2), and the structural unit (A2) further includes the structural unit (A21) derived from the compound represented by the following formula (a21). It is more preferable that A further contains a structural unit (A2), and the structural unit (A2) includes a structural unit (A22) derived from a compound represented by the following formula (a22).
  • 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
  • specific examples thereof include 3,3', 4,4'-biphenyl represented by the following formula (a21s).
  • a-BPDA 2,2,', 3,3'-biphenyltetracarboxylic dianhydride represented.
  • the compound represented by the formula (a22) is 9,9'-bis (3,4-dicarboxyphenyl) fluorene dianhydride.
  • the compound represented by the formula (a23) is 4,4'-(hexafluoroisopropyridene) diphthalic anhydride.
  • the content ratio of the structural unit (A1) in the structural unit A is preferably 50 mol% or more, more preferably 55 mol% or more, still more preferably 60 mol% or more, still more preferably 80 mol%. % Or more, more preferably 90 mol% or more, still more preferably 95 mol% or more.
  • the upper limit of the content ratio of the structural unit (A1) is not particularly limited, that is, 100 mol%.
  • the structural unit A may consist of only the structural unit (A1). By including the structural unit (A1) in the structural unit A at the above-mentioned content ratio, the colorless transparency and heat resistance are particularly excellent.
  • the ratio of the structural unit (A2) in the structural unit A is preferably 5 to 50 mol%, more preferably 10 to 40 mol%, and further preferably. Is 15-35 mol%.
  • the molar ratio [(A1) / (A2)] of the constituent unit (A1) to the constituent unit (A2) is preferably 50/50 to 95/5. It is more preferably 60/40 to 90/10, and even more preferably 65/35 to 85/15.
  • the structural unit A may include a structural unit other than the structural units (A1) and (A2).
  • the tetracarboxylic dianhydride forming such a structural unit is not particularly limited, but is an aromatic tetracarboxylic dianhydride such as pyromellitic dianhydride (however, a compound represented by the formula (a2)).
  • alicyclic tetracarboxylic dianhydrides such as 1,2,3,4-cyclobutanetetracarboxylic dianhydrides and 1,2,4,5-cyclohexanetetracarboxylic dianhydrides (provided that the formula is (Excluding the compound represented by (a1)); and aliphatic tetracarboxylic dianhydrides such as 1,2,3,4-butanetetracarboxylic dianhydride.
  • the aromatic tetracarboxylic dianhydride means a tetracarboxylic dianhydride containing one or more aromatic rings, and the alicyclic tetracarboxylic dianhydride has one alicyclic ring.
  • the structural unit other than the structural unit (A1) arbitrarily included in the structural unit A may be one type or two or more types.
  • the structural unit B is a structural unit derived from a diamine, and includes a structural unit (B1) derived from a compound represented by the formula (b1).
  • the structural unit (B1) improves heat resistance, elongation, and colorless transparency, but above all, elongation is improved, and colorlessness is also improved.
  • the compound represented by the formula (b1) is 2,2'-bis (trifluoromethyl) -4,4'-diaminodiphenyl ether (6FODA).
  • the structural unit B may include a structural unit other than the structural unit (B1).
  • the structural unit B preferably further includes a structural unit (B2) in addition to the structural unit (B1).
  • the structural unit (B2) is selected from the group consisting of the structural unit (B21) derived from the compound represented by the following formula (b21) and the structural unit (B22) derived from the compound represented by the following formula (b22). At least one is preferable.
  • the heat resistance is particularly improved, and the elastic modulus is also improved.
  • the structural unit (B2) is preferably a structural unit (B22) derived from the compound represented by the formula (b22) from the viewpoint of improving transparency, dimensional stability against heat, and elastic modulus.
  • the structural unit B further includes the structural unit (B2), and the structural unit (B2) includes the structural unit (B22) derived from the compound represented by the following formula (b22).
  • the structural unit (B2) is preferably a structural unit (B21) derived from the compound represented by the formula (b21), and the structural unit (B21) particularly improves heat resistance and elastic modulus.
  • the compound represented by the formula (b21) is 9,9-bis (4-aminophenyl) fluorene.
  • the compound represented by the formula (b22) is 2,2'-bis (trifluoromethyl) benzidine.
  • the content ratio of the structural unit (B1) in the structural unit B is preferably 10 mol% or more, more preferably 20 mol% or more, still more preferably 30 mol% or more, still more preferably 50 mol. % Or more, more preferably 60 mol% or more, still more preferably 80 mol% or more.
  • the upper limit of the content ratio of the structural unit (B1) is not particularly limited, that is, 100 mol%.
  • the structural unit B may consist of only the structural unit (B1). By including the structural unit (B1) in the structural unit B in the above-mentioned content ratio, the elongation is particularly improved, and the colorlessness is also improved.
  • the ratio of the structural unit (B2) in the structural unit B is preferably 1 to 90 mol%, more preferably 1 to 80 mol%, and further preferably. Is 2 to 70 mol%, more preferably 3 to 50 mol%, even more preferably 4 to 40 mol%, and even more preferably 5 to 20 mol%.
  • the constituent unit B includes the constituent unit (B2)
  • the molar ratio [(B1) / (B2)] of the constituent unit (B1) to the constituent unit (B2) is determined from the viewpoint of colorlessness, elongation, and transparency.
  • the molar ratio of the structural unit (B1) to the structural unit (B2) [(B1) / (B2)] is preferably 10/90 to 60/40, more preferably 10/90 to 50/50, still more preferably 10/90 to 40/60, and even more preferably 10/90. It is 90 to 30/70, more preferably 10/90 to 20/80, and even more preferably 10/90 to 15/85.
  • the constituent unit B includes the constituent unit (B2) and the constituent unit (B2) includes the constituent unit (B22)
  • the constituent unit (B1) and the constituent unit (B22) are particularly from the viewpoint of colorlessness, elongation, and transparency.
  • the molar ratio [(B1) / (B22)] is preferably 10/90 to 99/1, more preferably 20/80 to 99/1, and even more preferably 30/70 to 98/2. Yes, more preferably 50/50 to 97/3, even more preferably 60/40 to 96/4, and even more preferably 80/20 to 95/5.
  • the molar ratio of the structural unit (B1) to the structural unit (B22) [(B1) / (B22)] is preferably 10/90 to 60/40, more preferably 10/90 to 50/50, still more preferably 10/90 to 40/60, and even more preferably 10/90. It is 90 to 30/70, more preferably 10/90 to 20/80, and even more preferably 10/90 to 15/85.
  • the structural unit B may include a structural unit other than the structural units (B1) and (B2).
  • the diamine forming such a constituent unit is not particularly limited, but is limited to 1,4-phenylenediamine, p-xylylene diamine, 3,5-diaminobenzoic acid, and 2,2'-dimethylbiphenyl-4,4'.
  • 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 other than the structural unit (B1) arbitrarily included in the structural unit B may be one type or two or more types.
  • the number average molecular weight of the polyimide resin of the present invention is preferably 5,000 to 200,000 from the viewpoint of the mechanical strength of the obtained polyimide film.
  • the number average molecular weight of the polyimide resin can be obtained from, for example, a standard polymethylmethacrylate (PMMA) conversion value measured by gel filtration chromatography.
  • the polyimide resin of the present invention has both heat resistance and elongation, and is also excellent in colorless transparency, and can have the following physical property values.
  • the polyimide resin of the present invention has a total light transmittance of preferably 85% or more, more preferably 88% or more, still more preferably 90% or more, and more when it is made into a polyimide film having a thickness of 10 ⁇ m. More preferably, it is 91% or more.
  • the polyimide resin of the present invention has a yellow index (YI) of preferably 3.5 or less, more preferably 3.0 or less, still more preferably 2.0 or less when a polyimide film having a thickness of 10 ⁇ m is formed. Is.
  • the glass transition temperature (Tg) of the polyimide resin of the present invention is preferably 350 ° C. or higher, more preferably 380 ° C. or higher, further preferably 400 ° C. or higher, and even more preferably 430 ° C. or higher.
  • the total light transmittance, the yellow index (YI), and the glass transition temperature (Tg) in the present invention can be specifically measured by the methods described in Examples.
  • the polyimide resin of the present invention can be produced by reacting a tetracarboxylic acid component containing the compound giving the above-mentioned structural unit (A1) with a diamine component containing the compound giving the above-mentioned structural unit (B1). can.
  • Examples of the compound that gives the structural unit (A1) include the compound represented by the formula (a1), but the compound is not limited to this, and may be a derivative thereof as long as the same structural unit can be formed.
  • the tetracarboxylic dian corresponding to the compound represented by the formula (a1) that is, norbornane-2-spiro- ⁇ -cyclopentanone- ⁇ '-spiro-2''-norbornane-5,5' ', 6, 6''-tetracarboxylic dian
  • alkyl esters of the tetracarboxylic dian As the compound giving the structural unit (A1), the compound represented by the formula (a1) (that is, tetracarboxylic dianhydride) is preferable.
  • the tetracarboxylic acid component may contain a compound other than the compound that gives the structural unit (A1).
  • the tetracarboxylic acid component preferably contains a compound that further gives a constituent unit (A2) in addition to the compound that gives the constituent unit (A1).
  • Examples of the compound giving the structural unit (A2) include the compound represented by the formula (a2), but the compound is not limited to this, and may be a derivative thereof as long as the same structural unit can be formed. Examples of the derivative include a tetracarboxylic acid corresponding to the compound represented by the formula (a2) and an alkyl ester of the tetracarboxylic acid.
  • the compound represented by the formula (a2) (that is, tetracarboxylic dianhydride) is preferable.
  • the compound that gives the structural unit (A2) is a compound that gives the structural unit (A21) represented by the formula (a21), a compound that gives the structural unit (A22) represented by the formula (a22), and a compound that gives the structural unit (A22) represented by the formula (a23). It is preferably at least one selected from the group consisting of the compound giving the structural unit (A23) represented, and is selected from the group consisting of the compound giving the structural unit (A21) and the compound giving the structural unit (A22). It is preferably at least one, more preferably a compound giving a constituent unit (A21) from the viewpoint of improving elongation, and more preferably a compound giving a constituent unit (A22) from the viewpoint of heat resistance. preferable.
  • the tetracarboxylic acid component contains a compound that gives the structural unit (A1) in an amount of preferably 50 mol% or more, more preferably 55 mol% or more, still more preferably 60 mol% or more, still more preferably 80 mol% or more. It contains, more preferably 90 mol% or more, and even more preferably 95 mol% or more.
  • the upper limit of the content ratio of the compound giving the structural unit (A1) is not particularly limited, that is, 100 mol%.
  • the tetracarboxylic acid component may consist only of the compound giving the structural unit (A1).
  • the tetracarboxylic acid component when the tetracarboxylic acid component contains a compound that gives the structural unit (A2), the tetracarboxylic acid component preferably contains 5 to 50 mol%, more preferably 10 to 40 mol%, of the compound that gives the structural unit (A2). Includes, more preferably 15-35 mol%.
  • the molar ratio [(A1) / (A2)] of the compound that gives the structural unit (A1) to the compound that gives the structural unit (A2) is preferable. It is 50/50 to 95/5, more preferably 60/40 to 90/10, and even more preferably 65/35 to 85/15.
  • the tetracarboxylic acid component may contain a compound other than the compound giving the structural unit (A1) and the compound giving the structural unit (A2), and the compound includes the above-mentioned aromatic tetracarboxylic dianhydride and alicyclic type. Examples thereof include tetracarboxylic dianhydride, aliphatic tetracarboxylic dianhydride, and derivatives thereof (tetracarboxylic dian, alkyl ester of tetracarboxylic dian, etc.).
  • the compound arbitrarily contained in the tetracarboxylic acid component (that is, the compound other than the compound giving the structural unit (A1)) may be one kind or two or more kinds.
  • Examples of the compound that gives the structural unit (B1) include the compound represented by the formula (b1), but the compound is not limited to this, and may be a derivative thereof as long as the same structural unit can be formed.
  • Examples of the derivative include diisocyanate corresponding to the compound represented by the formula (b1).
  • the compound represented by the formula (b1) that is, a diamine is preferable.
  • the diamine component may contain a compound other than the compound that gives the structural unit (B1).
  • the diamine component preferably contains, in addition to the compound that gives the structural unit (B1), a compound that further gives the structural unit (B2).
  • the compound that gives the structural unit (B2) is preferably a compound that gives the structural unit (B22) represented by the formula (b22) from the viewpoint of improving transparency, dimensional stability against heat, and elastic modulus. From the viewpoint of improving heat resistance and elastic modulus, the structural unit (B2) is preferably a compound that gives the structural unit (B21) represented by the formula (b21).
  • Examples of the compound giving the structural unit (B2) include, but are not limited to, the compound represented by the formula (b21) and the compound represented by the formula (b22), and the derivative thereof within the range in which the same structural unit can be formed. There may be.
  • Examples of the derivative include diisocyanate corresponding to the compound represented by the formula (b21) and diisocyanate corresponding to the compound represented by the formula (b22).
  • a compound represented by the formula (b21) and a compound represented by the formula (b22) that is, a diamine are preferable.
  • the diamine component preferably contains a compound that gives the structural unit (B1) in an amount of 10 mol% or more, more preferably 20 mol% or more, further preferably 30 mol% or more, still more preferably 50 mol% or more. Even more preferably, it contains 60 mol% or more, and even more preferably 80 mol% or more.
  • the upper limit of the content ratio of the compound giving the structural unit (B1) is not particularly limited, that is, 100 mol%.
  • the diamine component may consist only of a compound that gives the structural unit (B1).
  • the diamine component when the diamine component contains a compound that gives the structural unit (B2), the diamine component preferably contains 1 to 90 mol%, more preferably 1 to 80 mol%, and more preferably the compound that gives the structural unit (B2). Contains 2 to 70 mol%, more preferably 3 to 50 mol%, even more preferably 4 to 40 mol%, still more preferably 5 to 20 mol%.
  • the diamine component contains a compound that gives a constituent unit (B2)
  • ) / (B2)] is preferably 10/90 to 99/1, more preferably 20/80 to 99/1, still more preferably 30/70 to 98/2, and even more preferably. It is 50/50 to 97/3, more preferably 60/40 to 96/4, and even more preferably 80/20 to 95/5. Further, from the viewpoint of improving mechanical properties such as elastic modulus, heat resistance, and thermal properties such as dimensional stability with respect to heat, the molars of the compound giving the structural unit (B1) and the compound giving the structural unit (B2).
  • the ratio [(B1) / (B2)] is preferably 10/90 to 60/40, more preferably 10/90 to 50/50, and even more preferably 10/90 to 40/60. It is even more preferably 10/90 to 30/70, even more preferably 10/90 to 20/80, and even more preferably 10/90 to 15/85.
  • the molar ratio [(B1) / (B22)] of the compound giving B1) to the compound giving the structural unit (B22) is preferably 10/90 to 99/1, more preferably 20/80 to 99/1. It is more preferably 30/70 to 98/2, even more preferably 50/50 to 97/3, even more preferably 60/40 to 96/4, and even more preferably 80/ It is 20 to 95/5.
  • the ratio [(B1) / (B22)] is preferably 10/90 to 60/40, more preferably 10/90 to 50/50, and even more preferably 10/90 to 40/60. It is even more preferably 10/90 to 30/70, even more preferably 10/90 to 20/80, and even more preferably 10/90 to 15/85.
  • the diamine component may contain a compound that gives the constituent unit (B1) and a compound other than the compound that gives the constituent unit (B2), and the compounds include the above-mentioned aromatic diamine, alicyclic diamine, and aliphatic diamine, and Examples thereof include derivatives (diamines and the like).
  • the compound arbitrarily contained in the diamine component (that is, the compound other than the compound giving the structural unit (B1)) may be one kind or two or more kinds.
  • the ratio of the amount of the tetracarboxylic acid component to the diamine component charged in the production of the polyimide resin 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 polyimide resin.
  • the terminal encapsulant monoamines or dicarboxylic acids are preferable.
  • the amount of the terminal encapsulant 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 the monoamine terminal encapsulant 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, cyclohexane-1,2-dicarboxylic acid, cyclopentane-1,2 -Dicarboxylic acid, 4-cyclohexene-1,2-dicarboxylic acid and the like are recommended.
  • phthalic acid and phthalic anhydride can be preferably used.
  • the method for reacting the above-mentioned tetracarboxylic acid component with the diamine component 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 0 to 80 ° 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 0 to 80 ° 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 reaction solvent used in the production of the polyimide resin may be one that does not inhibit the imidization reaction and can dissolve the produced polyimide.
  • 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 based solvents, ketone solvents such as acetone, cyclohexanone and methylcyclohexanone, amine solvents such as picolin and pyridine, and ester solvents 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.
  • the above-mentioned reaction solvent may be used alone or in mixture of 2 or more types.
  • 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 more preferably an organic base catalyst, further preferably triethylamine, and particularly preferably a combination of triethylamine and triethylenediamine.
  • 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 polyimide varnish of the present invention is obtained by dissolving the polyimide resin of the present invention in an organic solvent. That is, the polyimide varnish of the present invention contains the polyimide resin of the present invention and an organic solvent, and the polyimide resin is dissolved in the organic solvent.
  • the organic solvent may be any one that dissolves the polyimide resin, and is not particularly limited, but it is preferable to use the above-mentioned compounds alone or in combination of two or more as the reaction solvent used for producing the polyimide resin. Since the polyimide resin of the present invention has solvent solubility, it is possible to obtain a high-concentration varnish that is stable at room temperature.
  • the polyimide varnish of the present invention preferably contains the polyimide resin of the present invention in an amount of 3 to 40% by mass, more preferably 5 to 30% by mass.
  • the viscosity of the polyimide varnish is preferably 0.1 to 200 Pa ⁇ s, more preferably 0.5 to 150 Pa ⁇ s.
  • the polyimide varnish of the present invention contains an inorganic filler, an adhesion accelerator, a release agent, a flame retardant, an ultraviolet stabilizer, a surfactant, a leveling agent, a defoaming agent, and an optical brightener as long as the required properties of the polyimide film are not impaired.
  • Various additives such as a whitening agent, a cross-linking agent, a polymerization initiator, and a photosensitizer may be contained.
  • the method for producing the polyimide varnish of the present invention is not particularly limited, and a known method can be applied.
  • the polyimide film of the present invention contains the polyimide resin of the present invention. Therefore, the polyimide film of the present invention has good heat resistance and elongation, and is also excellent in colorless transparency.
  • the method for producing the polyimide film (production method) of the present invention is not particularly limited, and a known method can be used. For example, a method of removing the organic solvent after applying or molding the polyimide varnish of the present invention into a film form can be mentioned. From the viewpoint of obtaining a smooth film having a desired thickness, the polyimide varnish of the present invention is formed into a film form. A method of removing the organic solvent after coating or molding is preferable.
  • the polyimide film of the present invention Since the polyimide film of the present invention has good heat resistance and elongation, and is also excellent in colorless transparency, it can be used as a film for various members such as color filters, flexible displays, semiconductor parts, and optical members. It is preferably used.
  • 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.
  • Solid content concentration The solid content concentration of the varnish was measured by heating the sample at 320 ° C. ⁇ 120 min in a small electric furnace “MMF-1” manufactured by AS ONE Corporation, and calculating from the mass difference of the sample before and after heating.
  • Film thickness The film thickness was measured using a micrometer manufactured by Mitutoyo Co., Ltd.
  • Total light transmittance, yellow index (YI) The measurement was carried out in accordance with JIS K7361-1 using a color / turbidity simultaneous measuring device "COH400" manufactured by Nippon Denshoku Industries Co., Ltd.
  • CTE Coefficient of linear thermal expansion
  • the elastic modulus and strength are tensile elastic modulus and tensile strength according to JIS K7127, and were measured using a tensile tester "Strograph VG-1E” manufactured by Toyo Seiki Co., Ltd.
  • Elongation Elongation was performed by a tensile test (measurement of elongation) in accordance with JIS K7127.
  • the test piece used had a width of 10 mm and a thickness of 10 to 60 ⁇ m.
  • tetracarboxylic acid component and diamine component used in Examples and Comparative Examples, and their abbreviations and the like are as follows.
  • ⁇ Tetracarboxylic acid component> CpODA: Norbornane-2-spiro- ⁇ -cyclopentanone- ⁇ '-spiro-2''-norbornane-5,5'', 6,6''-tetracarboxylic dianhydride (manufactured by JX Energy Co., Ltd .; Compound represented by formula (a1)) s-BPDA: 3,3', 4,4'-biphenyltetracarboxylic dianhydride (compound represented by the formula (a21s)) BPAF :: 9,9'-bis (3,4-dicarboxyphenyl) fluorene dianhydride (manufactured by JFE Chemical Co., Ltd .; compound represented by formula (a22)) TAHQ: p-phenylenebis (trimeritate) dianhydr
  • NMP N-methyl-2-pyrrolidone (manufactured by Mitsubishi Chemical Corporation)
  • GBL ⁇ -Butyrolactone (manufactured by Mitsubishi Chemical Corporation)
  • TEDA Triethylenediamine TEA: Triethylamine
  • Example 1 33.624 g (0.100 mol) of 6FODA in a 500 mL five-necked round-bottom flask equipped with a stainless steel half-moon agitator, a nitrogen inlet tube, a Dean Stark with a cooling tube, a thermometer, and a glass end cap. And GBL was added in an amount of 86.474 g, 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 Same as Example 1 except that the amount of CpODA was changed from 38.438 g (0.100 mol) to 30.750 g (0.080 mol) and 5.884 g (0.020 mol) of s-BPDA was added.
  • a polyimide varnish was prepared by the above method to obtain a polyimide varnish having a solid content concentration of 15% by mass. Using the obtained polyimide varnish, a film was obtained by the same method as in Example 1.
  • Example 3 The same method as in Example 1 except that the amount of 6FODA was changed from 33.624 g (0.100 mol) to 3.362 g (0.010 mol) and 28.822 g (0.090 mol) of TFMB was added. To prepare a polyimide varnish, a polyimide varnish having a solid content concentration of 15% by mass was obtained. Using the obtained polyimide varnish, a film was obtained by the same method as in Example 1.
  • Example 4 The same method as in Example 1 except that the amount of 6FODA was changed from 33.624 g (0.100 mol) to 6.725 g (0.020 mol) and 25.619 g (0.080 mol) of TFMB was added. To prepare a polyimide varnish, a polyimide varnish having a solid content concentration of 15% by mass was obtained. Using the obtained polyimide varnish, a film was obtained by the same method as in Example 1.
  • Example 5 The same method as in Example 1 except that the amount of 6FODA was changed from 33.624 g (0.100 mol) to 16.812 g (0.050 mol) and 16.012 g (0.050 mol) of TFMB was added. To prepare a polyimide varnish, a polyimide varnish having a solid content concentration of 15% by mass was obtained. Using the obtained polyimide varnish, a film was obtained by the same method as in Example 1.
  • Example 6> The amount of 6FODA was changed from 33.624 g (0.100 mol) to 20.174 g (0.060 mol), BAFL was added 13.938 g (0.040 mol), and the amount of CpODA was 38.438 g (0).
  • a polyimide varnish was prepared by the same method as in Example 1 except that 11.769 g (0.040 mol) of s-BPDA was added by changing from (100 mol) to 23.063 g (0.060 mol). A polyimide varnish having a solid content concentration of 15% by mass was obtained. Using the obtained polyimide varnish, a film was obtained by the same method as in Example 1.
  • Example 7 Change the amount of 6FODA from 33.624 g (0.100 mol) to 18.493 g (0.055 mol), add 15.680 g (0.045 mol) of BAFL, and increase the amount of CpODA to 38.438 g (0).
  • a polyimide varnish was prepared by the same method as in Example 1 except that the amount was changed from (100 mol) to 34.594 g (0.090 mol) and 4.584 g (0.010 mol) of BPAF was added. A polyimide varnish having a concentration of 15% by mass was obtained. Using the obtained polyimide varnish, a film was obtained by the same method as in Example 1.
  • the obtained polyamic acid varnish was applied onto a glass plate by spin coating, held at 80 ° C. for 20 minutes on a hot plate, and then heated at 400 ° C. for 30 minutes in a hot air dryer under a nitrogen atmosphere (ascending). The solvent was evaporated at a temperature rate of 5 ° C./min) and further thermally imidized to obtain a polyimide film.
  • a polyamic acid varnish was prepared by the same method as in Comparative Example 2 except that 38.438 g (0.100 mol) of CpODA was changed to 45.833 g (0.100 mol) of TAHQ, and a polyamide having a solid content concentration of 15% by mass was prepared. Obtained acid varnish. Using the obtained polyamic acid varnish, a polyimide film was obtained by the same method as in Comparative Example 2.
  • the polyimide film of the example has good heat resistance and elongation, and is also excellent in colorless transparency.

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  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)

Abstract

L'invention concerne une résine polyimide comprenant une unité structurale A dérivée d'un dianhydride d'acide tétracarboxylique et une unité structurale B dérivée d'une diamine, l'unité structurale A comprenant une unité structurale (A1) dérivée d'un composé représenté par la formule (a1) et l'unité structurale B comprenant une unité structurale (B1) dérivée d'un composé représenté par la formule (b1).
PCT/JP2021/001883 2020-01-31 2021-01-20 Résine polyimide, vernis polyimide et film polyimide WO2021153379A1 (fr)

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CN105461923A (zh) * 2015-12-25 2016-04-06 南京理工大学 一种聚酰亚胺薄膜及其制备方法
WO2017191822A1 (fr) * 2016-05-06 2017-11-09 三菱瓦斯化学株式会社 Résine de polyimide
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JP2018066017A (ja) * 2012-05-28 2018-04-26 宇部興産株式会社 ポリイミド前駆体及びポリイミド
JP2019112632A (ja) * 2017-12-22 2019-07-11 ドゥーサン コーポレイション ポリアミック酸溶液及びこれを用いた透明ポリイミド樹脂フィルム
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KR102345844B1 (ko) * 2014-03-31 2021-12-31 닛산 가가쿠 가부시키가이샤 수지 박막의 제조방법 및 수지 박막형성용 조성물
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JP2018066017A (ja) * 2012-05-28 2018-04-26 宇部興産株式会社 ポリイミド前駆体及びポリイミド
JP2015108092A (ja) * 2013-12-05 2015-06-11 学校法人東京工芸大学 ポリイミドの製造方法及びその製造方法により得られるポリイミド
CN105461923A (zh) * 2015-12-25 2016-04-06 南京理工大学 一种聚酰亚胺薄膜及其制备方法
WO2017191822A1 (fr) * 2016-05-06 2017-11-09 三菱瓦斯化学株式会社 Résine de polyimide
WO2018066522A1 (fr) * 2016-10-07 2018-04-12 Ｊｘｔｇエネルギー株式会社 Polyimide, résine de précurseur de polyimide, solution de ceux-ci, procédé de fabrication de polyimide, et film mettant en œuvre ce polyimide
JP2019112632A (ja) * 2017-12-22 2019-07-11 ドゥーサン コーポレイション ポリアミック酸溶液及びこれを用いた透明ポリイミド樹脂フィルム
CN110396194A (zh) * 2019-09-06 2019-11-01 株洲时代新材料科技股份有限公司 一种含氟耐磨聚酰胺酰亚胺材料及其制备方法

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