Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/49—Phosphorus-containing compounds
  • C08K5/51—Phosphorus bound to oxygen
  • C08K5/52—Phosphorus bound to oxygen only
  • C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
• • 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
  • 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
  • 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
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
  • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
  • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D179/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09D161/00 - C09D177/00
  • C09D179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
  • C09D179/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • 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 polymer composition, a varnish, and a polyimide film.
• the polyimide resin Since the polyimide resin has excellent mechanical properties and heat resistance, various uses are being studied in the fields of electric and electronic parts 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 polyimide film substrate, and a polyimide resin satisfying the performance as an optical material is being developed.
• a polyimide resin satisfying the performance as an optical material is being developed.
• Patent Document 1 contains a specific polyamic acid and a specific phosphorus compound for the purpose of preventing crystallization and shortening the layer formation time in addition to heat resistance and mechanical properties.
• a polyimide precursor composition capable of producing a polyimide film having a large water vapor permeability coefficient by heat treatment under a condition where the maximum heating temperature is 300 to 500 ° C.
• Patent Document 2 contains a polyimide precursor having a specific repeating unit and a phosphorus atom for the purpose of obtaining a polyimide having transparency, heat resistance, and a low coefficient of linear thermal expansion, and has a boiling point at 1 atm.
• a polyimide precursor composition containing a phosphorus compound having a decomposition temperature lower than the decomposition temperature and 350 ° C. or lower is disclosed.
• the polyimide film is required to replace the glass substrate, and is required to have not only mechanical properties and heat resistance but also high colorless transparency. Further, when manufacturing an image display device, for example, since heat treatment is performed in a state where an inorganic film is laminated on polyimide in the TFT step, outgas generated from the polyimide accumulates between the polyimide and the inorganic film, which causes yellowing. May occur, and it is required that there is no change in hue by heat treatment in a state where the inorganic films are laminated. However, it is difficult to achieve both of these performances, and it is difficult to prevent yellowing even if the heat resistance is improved by adding an additive.
• an aliphatic diamine or a fluorine-containing diamine is generally used in order to suppress the formation of an intramolecular or intramolecular charge transfer complex.
• the aliphatic diamine lacks rigidity as compared with the aromatic diamine, so that it is difficult to develop heat resistance, and it also contains.
• Fluorodiamine also has a problem that yellowing occurs at high temperatures. Therefore, there has been a demand for a polyimide film having particularly excellent heat resistance, little change in hue after heat treatment, and a low yellowness.
• the present invention has been made in view of such a situation, and the subject of the present invention is a polymer composition capable of obtaining a polyimide film having excellent heat resistance, little change in hue after heat treatment, and a low yellowness. It is an object of the present invention to provide a product, a varnish containing the composition, and a polyimide film having excellent heat resistance and a low yellowness.
• the present inventors have determined that a polymer composition containing a specific fluorine-containing diamine and a repeating unit derived from a tetracarboxylic acid having an alicyclic structure or an aromatic ring and a specific phosphorus compound can solve the above-mentioned problems. I found it and came to complete the invention.
• X 1 is a tetravalent group having an alicyclic structure or an aromatic ring
• X is a group consisting of a single bond, -NHCO-, -CONH-, -COO- and -OCO-. At least one chosen.
• X 2 is a tetravalent group having an alicyclic structure or an aromatic ring, and R 1 and R 2 are independently hydrogen, an alkyl group having 1 to 6 carbon atoms, or an alkyl group having 3 to 3 carbon atoms, respectively. It is an alkylsilyl group of 9, and X is at least one selected from the group consisting of a single bond, -NHCO-, -CONH-, -COO- and -OCO-.
• R 3 is at least one selected from the group consisting of an alkyl group having 1 to 30 carbon atoms, a phenyl group, an alkoxy group, an acryloyl group, a methacryloyl group, an acryloyloxyethyl group, and a methacryloyloxyethyl group.
• n is 0 to 2.
• the polymer (X) contains at least one selected from the group consisting of the repeating unit represented by the following general formula (1-2) and the repeating unit represented by the following general formula (2-2). , The polymer composition according to the above [1].
• X 1 is a tetravalent group having an alicyclic structure or an aromatic ring, and X is composed of a single bond, -NHCO-, -CONH-, -COO- and -OCO-. At least one selected from the group.
• X 2 is a tetravalent group having an alicyclic structure or an aromatic ring, and R 1 and R 2 are independently hydrogen and carbon atoms, respectively.
• X 1 is a tetravalent group having an alicyclic structure or an aromatic ring.
• X 2 is an alicyclic structure or an aromatic ring.
• R 1 and R 2 are independently hydrogen, an alkyl group having 1 to 6 carbon atoms, or an alkylsilyl group having 3 to 9 carbon atoms, respectively.
• a polymer composition having excellent heat resistance, little change in hue after heat treatment, and a polyimide film having a low yellowness can be obtained, a varnish containing the composition, and heat treatment having excellent heat resistance. It is possible to provide a polyimide film having a low degree of yellowness with little change in hue afterwards.
• the polymer composition of the present invention contains at least one selected from the group consisting of a repeating unit represented by the following general formula (1) and a repeating unit represented by the following general formula (2) (X). And the compound (Y) represented by the following general formula (3).
• X 1 is a tetravalent group having an alicyclic structure or an aromatic ring
• X is a group consisting of a single bond, -NHCO-, -CONH-, -COO- and -OCO-. At least one chosen.
• X 2 is a tetravalent group having an alicyclic structure or an aromatic ring, and R 1 and R 2 are independently hydrogen, an alkyl group having 1 to 6 carbon atoms, or an alkyl group having 3 to 3 carbon atoms, respectively. It is an alkylsilyl group of 9, and X is at least one selected from the group consisting of a single bond, -NHCO-, -CONH-, -COO- and -OCO-.
• R 3 is at least one selected from the group consisting of an alkyl group having 1 to 30 carbon atoms, a phenyl group, an alkoxy group, an acryloyl group, a methacryloyl group, an acryloyloxyethyl group, and a methacryloyloxyethyl group.
• n is 0 to 2.
• the polymer composition of the present invention contains a specific phosphorus compound, but the phosphorus compound is coordinated to the end of the polyimide obtained by imidizing the polymer, or the end of the polyimide reacts with the phosphorus compound.
• side reactions or decomposition deterioration of the terminal at high temperature can be suppressed, and further, desorption of fluorine derived from fluorine-containing diamine can be suppressed, thereby achieving both heat resistance and low yellowness. It is considered that the color change can be suppressed even if the heat treatment is further performed.
• the polymer (X) contained in the polymer composition of the present invention is at least one selected from the group consisting of a repeating unit represented by the following general formula (1) and a repeating unit represented by the following general formula (2). Including one.
• X 1 is a tetravalent group having an alicyclic structure or an aromatic ring
• X is a group consisting of a single bond, -NHCO-, -CONH-, -COO- and -OCO-. At least one chosen.
• X 2 is a tetravalent group having an alicyclic structure or an aromatic ring, and R 1 and R 2 are independently hydrogen, an alkyl group having 1 to 6 carbon atoms, or an alkyl group having 3 to 3 carbon atoms, respectively. It is an alkylsilyl group of 9, and X is at least one selected from the group consisting of a single bond, -NHCO-, -CONH-, -COO- and -OCO-. )
• X in the formula (1) is preferably a single bond from the viewpoint of heat resistance. Further, X in the formula (2) is preferably a single bond from the viewpoint of heat resistance. It is more preferable that both X in the formula (1) and the formula (2) are single bonds.
• the polymer (X) contained in the polymer composition of the present invention comprises a repeating unit represented by the following general formula (1-1) and a repeating unit represented by the following general formula (2-1). It is preferable to include at least one selected from the group.
• X 1 is a tetravalent group having an alicyclic structure or an aromatic ring.
• X 2 is a tetravalent group having an alicyclic structure or an aromatic ring, and R 1 and R 2 are independently hydrogen, an alkyl group having 1 to 6 carbon atoms, or a carbon number of carbon atoms, respectively. It is an alkylsilyl group of 3-9.
• the repeating unit represented by the general formula (1) contained in the polymer (X) is preferably a repeating unit represented by the following general formula (1-2).
• X 1 is a tetravalent group having an alicyclic structure or an aromatic ring, and X is composed of a single bond, -NHCO-, -CONH-, -COO- and -OCO-. At least one selected from the group.
• Examples of the repeating unit represented by the formula (1-2) contained in the polymer (X) include repeating units represented by the following formulas (1-2-1) to (1-2-5). From the viewpoint of heat resistance, the repeating unit represented by the formula (1-2-1) is preferable. That is, in the above formula (1-2), X is at least one selected from the group consisting of a single bond, -NHCO-, -CONH-, -COO- and -OCO-, but from the viewpoint of heat resistance. X is preferably a single bond. (In formulas (1-2-1) to (1-2-5), X 1 is a tetravalent group having an alicyclic structure or an aromatic ring.)
• the repeating unit represented by the general formula (2) contained in the polymer (X) is preferably a repeating unit represented by the following general formula (2-2).
• X 2 is a tetravalent group having an alicyclic structure or an aromatic ring, and R 1 and R 2 are independently hydrogen, an alkyl group having 1 to 6 carbon atoms, or carbon. It is an alkylsilyl group of number 3-9, where X is at least one selected from the group consisting of a single bond, -NHCO-, -CONH-, -COO- and -OCO-).
• Examples of the repeating unit represented by the formula (2-2) contained in the polymer (X) include repeating units represented by the following formulas (2-2-1) to (2-2-5). From the viewpoint of heat resistance, the repeating unit represented by the formula (2-2-1) is preferable. That is, in the above formula (2-2), X is at least one selected from the group consisting of a single bond, -NHCO-, -CONH-, -COO- and -OCO-, but from the viewpoint of heat resistance. X is preferably a single bond.
• X 2 is a tetravalent group having an alicyclic structure or an aromatic ring, and R 1 and R 2 are independently hydrogen and carbon, respectively. It is an alkyl group having 1 to 6 or an alkylsilyl group having 3 to 9 carbon atoms.
• the polymer (X) contained in the polymer composition of the present invention is a repeating unit represented by the following general formula (1-2) and a repeating unit represented by the following general formula (2-2). It is preferable to include at least one selected from the group consisting of units, from the repeating unit represented by the following general formula (1-2-1) and the repeating unit represented by the following general formula (2-2-1). It is more preferable to include at least one selected from the group.
• X 1 is a tetravalent group having an alicyclic structure or an aromatic ring, and X is composed of a single bond, -NHCO-, -CONH-, -COO- and -OCO-. At least one selected from the group.
• X 2 is a tetravalent group having an alicyclic structure or an aromatic ring, and R 1 and R 2 are independently hydrogen and carbon atoms, respectively. It is an alkyl group of 1 to 6 or an alkylsilyl group having 3 to 9 carbon atoms, and X is at least one selected from the group consisting of a single bond, -NHCO-, -CONH-, -COO- and -OCO-.
• X 1 is a tetravalent group having an alicyclic structure or an aromatic ring.
• X 2 is an alicyclic structure or an aromatic ring. It is a tetravalent group having a ring, and R 1 and R 2 are independently hydrogen, an alkyl group having 1 to 6 carbon atoms, or an alkylsilyl group having 3 to 9 carbon atoms, respectively.
• the polymer (X) contains at least one selected from the group consisting of the repeating unit represented by the general formula (1) and the repeating unit represented by the general formula (2). It may contain only one of the repeating unit represented by 1) or the repeating unit represented by the general formula (2), or may contain both. That is, the polymer composition of the present invention is a polyimide composition containing a polyimide containing a repeating unit represented by the following general formula (1) and a compound (Y) represented by the following general formula (3).
• X 1 is a tetravalent group having an alicyclic structure or an aromatic ring, and X is a group consisting of a single bond, -NHCO-, -CONH-, -COO- and -OCO-. At least one selected.
• R 3 is from an alkyl group having 1 to 30 carbon atoms, a phenyl group, an alkoxy group, an acryloyl group, a methacryloyl group, an acryloyloxyethyl group, and a methacryloyloxyethyl group.
• It is at least one selected from the group consisting of, and n is 0 to 2.
• It may be a polyamic acid composition containing a polyamic acid containing a repeating unit represented by the following general formula (2) and a compound (Y) represented by the following general formula (3).
• X 2 is a tetravalent group having an alicyclic structure or an aromatic ring, and R 1 and R 2 are independently hydrogen, an alkyl group having 1 to 6 carbon atoms, or 3 carbon atoms, respectively. 9 to 9 alkylsilyl groups, X is at least one selected from the group consisting of single bond, -NHCO-, -CONH-, -COO- and -OCO-.
• R 3 is.
• the polymer (X) preferably contains the repeating unit represented by the general formula (1), and more preferably the repeating unit represented by the general formula (1) and the repeating unit represented by the general formula (2). Includes both repeating units.
• X 1 is a tetravalent group having an alicyclic structure or an aromatic ring.
• 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 constituent unit A derived from the tetracarboxylic acid dianhydride described later. Is preferable.
• X 1 is a tetravalent group having an alicyclic structure or an aromatic ring.
• 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 constituent unit A derived from the tetracarboxylic acid dianhydride described later. Is preferable.
• X 2 is a tetravalent group having an alicyclic structure or an aromatic ring.
• 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 A derived from the tetracarboxylic acid dianhydride described later. Is preferable.
• R 1 and R 2 are independently hydrogen, an alkyl group having 1 to 6 carbon atoms, or an alkylsilyl group having 3 to 9 carbon atoms, and are preferably hydrogen.
• X 1 is a tetravalent group having an alicyclic structure or an aromatic ring.
• 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 constituent unit A derived from the tetracarboxylic acid dianhydride described later. Is preferable.
• the polymer (X) contains at least one selected from the group consisting of the repeating unit represented by the general formula (1) and the repeating unit represented by the general formula (2). It may contain only one of the repeating unit represented by the general formula (1) or the repeating unit represented by the general formula (2), and may contain both, but in particular, yellowness. From the viewpoint of reduction and improvement of transparency, the repeating unit represented by the formula (1) is preferably 10 mol% or more, more preferably 30 mol, based on all the repeating units of the polymer (X). % Or more, more preferably 50 mol% or more, still more preferably 70 mol% or more, still more preferably 90 mol% or more, and 100 mol% or less.
• the repeating unit represented by the formula (2) is preferably 10 mol% with respect to all the repeating units of the polymer (X). More preferably, it is 30 mol% or more, further preferably 50 mol% or more, further preferably 70 mol% or more, still more preferably 90 mol% or more, and 100 mol% or less. Is. Further, when both the repeating unit represented by the general formula (1) and the repeating unit represented by the general formula (2) are included, the repeating unit represented by the general formula (1) and the repeating unit represented by the general formula (1) are included.
• the molar ratio [(1) / (2)] of the repeating unit represented by 2) is preferably 10/90 to 70/30, more preferably 20/80 to 60/40, and even more preferably 20/80 to 60/40. It is 25/75 to 55/45.
• the polymer (X) contains at least one selected from the group consisting of the repeating unit represented by the general formula (1) and the repeating unit represented by the general formula (2), and constitutes the polymer.
• the structural unit to be used will be described below.
• the polymer (X) has a structural unit A derived from tetracarboxylic dianhydride and a structural unit B derived from diamine.
• the constituent unit A and the constituent unit B form an imide structure
• the repeating unit represented by the general formula (2) the constituent unit A and the constituent unit B are formed.
• the structural unit B forms an amic acid structure
• the structural unit derived from tetracarboxylic dianhydride is collectively referred to as the structural unit A
• the structural unit derived from the diamine is collectively referred to as the structural unit B.
• the structural unit A is a structural unit derived from tetracarboxylic acid dianhydride, and is a group consisting of a structural unit derived from the alicyclic tetracarboxylic acid dianhydride and a structural unit derived from aromatic tetracarboxylic acid dianhydride. At least one selected from the above, preferably a structural unit derived from alicyclic tetracarboxylic acid dianhydride from the viewpoint of low yellowness and transparency, and preferably aromatic tetracarboxylic from the viewpoint of heat resistance. It is a structural unit derived from acid dianhydride.
• Examples of the alicyclic tetracarboxylic acid dianhydride giving a structural unit derived from the alicyclic tetracarboxylic acid dianhydride include 1,2,4,5-cyclohexanetetracarboxylic acid dianhydride, 1,2,3.
• the compound is preferably represented by the following formula (a1), and the constituent unit A is preferably a constituent unit derived from the compound represented by the formula (a1).
• (A1) is included.
• 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.
• aromatic tetracarboxylic acid dianhydride giving a structural unit derived from the aromatic tetracarboxylic acid dianhydride
• aromatic tetracarboxylic acid dianhydride examples include biphenyltetracarboxylic acid dianhydride (BPDA) and 9,9-bis (3,4-dicarboxyphenyl).
• Fluolene dianhydride (BPAF), pyromellitic acid dianhydride, 3,3', 4,4'-(hexafluoroisopropylidene) diphthalic acid anhydride, 3,3', 4,4'-diphenylsulfone tetra
• BPAF Fluolene dianhydride
• pyromellitic acid dianhydride 3,3', 4,4'-(hexafluoroisopropylidene) diphthalic acid anhydride
• 3,3', 4,4'-diphenylsulfone tetra examples thereof include carboxylic acid dianhydride, 3,3', 4,4'-benzophenone tetracarboxylic acid dianhydride, 2,2', 3,3'-benzophenone tetracarboxylic acid dianhydride and the like.
• At least one selected from the group consisting of the compound represented by the following formula (a2) and the compound represented by the following formula (a3) is preferably selected from the viewpoint of achieving both heat resistance and low yellowness.
• a compound represented by the following formula (a2) that is, the structural unit A is preferably selected from the group consisting of the structural unit (A2) derived from the compound represented by the following formula (a2) and the structural unit (A3) derived from the compound represented by the following formula (a3). It contains at least one of the constituent units (A2) derived from the compound represented by the following formula (a2).
• the compound represented by the formula (a2) is biphenyltetracarboxylic acid dianhydride (BPDA), and specific examples thereof are 3,3', 4,4'-biphenyl represented by the following formula (a2s).
• BPDA biphenyltetracarboxylic acid dianhydride
• a-BPDA 2,3,3', 4'-biphenyltetracarboxylic acid dianhydride
• a2i examples thereof include 2,2', 3,3'-biphenyltetracarboxylic acid dianhydride (i-BPDA) represented.
• s-BPDA 3,3', 4,4'-biphenyltetracarboxylic dianhydride represented by the following formula (a2s) is preferable.
• the compound represented by the formula (a3) is 9,9'-bis (3,4-dicarboxyphenyl) fluorene dianhydride (BPAF).
• the repeating unit (polyimide unit) represented by the formula (1) includes at least one selected from the group consisting of the constituent unit (A1) and the constituent unit (A3), and is represented by the general formula (2).
• the repeating unit (polyimide unit) preferably contains a structural unit (A2).
• the structural unit A may contain a structural unit other than the aromatic tetracarboxylic dianhydride and the alicyclic tetracarboxylic dianhydride.
• the tetracarboxylic acid dianhydride giving such a structural unit is not particularly limited, and examples thereof include aliphatic tetracarboxylic acid dianhydrides such as 1,2,3,4-butanetetracarboxylic acid dianhydride.
• the structural unit arbitrarily included in the structural unit A may be one type or two or more types.
• the aromatic tetracarboxylic acid dianhydride means a tetracarboxylic acid dianhydride containing one or more aromatic rings, and the alicyclic tetracarboxylic acid dianhydride has one alicyclic ring.
• the tetracarboxylic acid dianhydride containing the above and containing no aromatic ring is meant, and the aliphatic tetracarboxylic acid dianhydride means a tetracarboxylic acid dianhydride containing neither an aromatic ring nor an alicyclic ring.
• the structural unit B is a structural unit derived from a diamine, and includes a structural unit (B1) derived from the compound represented by the formula (b1). By including the structural unit (B1) in the structural unit B, it is excellent in heat resistance, and particularly excellent in the effect of reducing the yellowness when combined with the compound (Y).
• the ratio of the structural unit (B1) in the structural unit B 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.
• X is at least one selected from the group consisting of single bond, -NHCO-, -CONH-, -COO- and -OCO-.
• the structural unit (B1) preferably includes a structural unit (B11) derived from the compound represented by the following formula (b11).
• the structural unit (B1) preferably contains a structural unit (B12) derived from the compound represented by the following formula (b12).
• X is at least one selected from the group consisting of a single bond, -NHCO-, -CONH-, -COO- and -OCO-.
• the structural unit (B12) is a structural unit (B121) derived from a compound represented by the following formula (b121), a structural unit (B122) derived from a compound represented by the following formula (b122), and the following formula (b123).
• b121 a structural unit derived from a compound represented by the following formula (b121)
• B122 a structural unit derived from a compound represented by the following formula (b122)
• b123 Contains at least one selected from the group consisting of the structural unit (B123) derived from the compound represented by the following formula (b121), and more preferably from the viewpoint of heat resistance.
• It is a structural unit (B121) containing a unit (B121) and more preferably derived from a compound represented by the following formula (b121).
• the compound represented by the formula (b121) is 2,2'-bis (trifluoromethyl) benzidine (TFMB).
• TFMB 2,2'-bis (trifluoromethyl) benzidine
• the structural unit B may include a structural unit other than the structural unit (B1).
• the diamine that gives such a constituent unit is not particularly limited, but is 3,5-diaminobenzoic acid (3,5-DABA), 9,9-bis (4-aminophenyl) fluorene (BAFL), 4-amino.
• Phenyl-4-aminobenzoate (4-BAAB), 1,4-phenylenediamine, p-xylylene diamine, 1,5-diaminonaphthalene, 2,2'-dimethylbiphenyl-4,4'-diamine, 2,2 '-Dimethylbiphenyl-4,4'-diamine, 4,4'-diaminodiphenylmethane, 1,4-bis [2- (4-aminophenyl) -2-propyl] benzene, 2,2-bis (4-amino) Phenyl) Hexafluoropropane, 4,4'-diaminobenzanilide, 1- (4-aminophenyl) -2,3-dihydro-1,3,3-trimethyl-1H-inden-5-amine, ⁇ , ⁇ ' -Bis (4-aminophenyl) -1,4-diisopropylbenzene, N, N'-bis (4-amin
• the compound is more preferably represented by the following formula (b21). That is, the structural unit B is preferably 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).
• the compound represented by the formula (b21) is 3,5-diaminobenzoic acid (3,5-DABA).
• the compound represented by the formula (b22) is 9,9-bis (4-aminophenyl) fluorene (BAFL).
• the molar ratio [(B1) / (B2)] of the constituent unit (B1) to the constituent unit (B2) is preferably 20/80 to 95/5. , More preferably 50/50 to 90/10, and even more preferably 70/30 to 90/10.
• the compound represented by the formula (b3) is 4-aminophenyl-4-aminobenzoate (4-BAAB).
• 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 does not contain 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 B may be one type or two or more types.
• the polymer (X) may be produced by any method, but the following method is preferable. As described above, the polymer (X) has a repeating unit represented by the general formula (1) (that is, an imide moiety) and a repeating unit represented by the general formula (2) (that is, an amide acid moiety). ), But these can be adjusted by changing the manufacturing method.
• the formula (by using only the step of manufacturing the portion (polyamide portion) mainly containing the repeating unit represented by 1), the polymer (X) (polyamide) substantially composed of the repeating unit represented by the formula (1) can be obtained.
• the polymer (2) substantially composed of the repeating unit represented by the formula (2) By using only the step of producing the obtained portion (polyamic acid moiety) mainly containing the repeating unit represented by the formula (2), the polymer (2) substantially composed of the repeating unit represented by the formula (2).
• X) (polyamic acid) can be obtained.
• the polymer (X) (hereinafter, also referred to as an imido-amide acid copolymer) containing both the repeating unit represented by the formula (1) and the repeating unit represented by the formula (2) is described in the following step 1 and the following steps 1. It is preferable to use the method having step 2.
• Step 1 Reacting the tetracarboxylic acid component constituting the imide moiety with the diamine component to obtain an imide oligomer
• Step 2 The imide oligomer obtained in Step 1 and the tetracarboxylic acid component constituting the amic acid moiety and Step of reacting diamine component to obtain imid-amide acid copolymer
• a polymer (X) (polyimide) consisting of a repeating unit substantially represented by the formula (1) can be obtained.
• the method for producing the polymer (X) (polyimide) substantially composed of the repeating unit represented by the formula (1) is described in the above step 1 as "a tetracarboxylic acid component constituting the polyimide and a diamine component”. It is read as "the process of obtaining polyimide by reacting with”.
• the polymer (X) (polyamic acid) composed of the repeating unit substantially represented by the formula (2).
• the method for producing the polymer (X) (polyamic acid), which is substantially composed of the repeating unit represented by the formula (2) describes the step 2 as "a tetracarboxylic acid component constituting the polyamic acid and a diamine.” It should be read as "the process of reacting the components to obtain polyamic acid”.
• Step 1 is a step of reacting the tetracarboxylic acid component constituting the imide moiety with the diamine component to obtain an imide oligomer.
• the tetracarboxylic acid component used in step 1 preferably contains a compound that gives a structural unit (A1), and it is preferable that the entire amount thereof is used in step 1, and tetracarboxylic dians other than the compound that gives the structural unit (A1). It may contain an acid component.
• a compound giving the structural unit (A2) or a compound giving the structural unit (A3) is preferable, and a compound giving the structural unit (A3) is more preferable.
• 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.
• a compound giving the structural unit (B2) or a compound giving the structural unit (B3) is preferable.
• 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 diamine component with respect to the tetracarboxylic acid component is 0.9 to 1.1 mol. Is preferable.
• the method for reacting the tetracarboxylic acid component and the diamine component for obtaining the imide oligomer in step 1 is not particularly limited, and a known method can be used.
• a specific reaction method (1) a tetracarboxylic acid component, a diamine component, and a reaction solvent are charged in a reactor, stirred at 10 to 110 ° C. for 0.5 to 30 hours, and then heated to imidize. Method of carrying out the reaction, (2) The diamine component and the reaction solvent are charged into a reactor and dissolved, then 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 or 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.
• organic base catalysts such as dimethylaniline and N, N-diethylaniline
• 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 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 further preferable, and triethylamine is further 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).
• 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 is a step of reacting the imide oligomer obtained in step 1 with the tetracarboxylic acid component and the diamine component constituting the amic acid moiety to obtain an imide-amide acid copolymer. ..
• the tetracarboxylic dian component used in step 2 preferably contains a compound that gives a structural unit (A1), and may contain a tetracarboxylic acid component other than the compound that gives the structural unit (A1).
• a compound giving the structural unit (A2) or a compound giving the structural unit (A3) is preferable.
• the tetracarboxylic dian component used in step 2 is preferably a compound giving a structural unit (A2).
• the diamine component used in step 2 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.
• a compound giving the structural unit (B2) or a compound giving the structural unit (B3) is preferable.
• the diamine component used in step 2 is preferably a compound giving a structural unit (B3).
• the diamine component with respect to the tetracarboxylic acid component is set to 0. It is preferably 9.9 to 1.1 mol.
• the method for reacting the tetracarboxylic acid component and the diamine component in step 2 with the imide oligomer obtained in step 1 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 method of stirring for about 72 hours (2) the imide oligomer and the solvent obtained in step 1 are charged into a reactor and dissolved, and then the tetracarboxylic acid component and the diamine component are charged, and the temperature is 0 to 120 ° C., preferably 5 to.
• Examples thereof include a method of stirring at 80 ° C. for 1 to 72 hours.
• the reaction is carried out at 80 ° C. or lower, the molecular weight of the copolymer obtained in step 2 does not fluctuate depending on the temperature history at the time of polymerization, and the progress of thermal imidization can be suppressed. Can be manufactured stably.
• a copolymer solution containing an imide-amide acid copolymer dissolved in a solvent can be obtained. Further, by performing only step 1, a polyimide solution containing polyimide can be obtained, and by performing only step 2, a polyamic acid solution containing polyamic acid can be obtained.
• the concentration of the copolymer in the obtained solution is usually 1 to 50% by mass, preferably 3 to 35% by mass, and more preferably 5 to 30% by mass.
• the concentration of polyimide in the obtained solution is usually 1 to 50% by mass, preferably 3 to 35% by mass, and more preferably 5 to 30% by mass. Further, the concentration of the polyamic acid in the obtained 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 above-mentioned production method 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 from the same viewpoint.
• the number average molecular weight and the weight average molecular weight of the copolymer can be obtained from, for example, standard polymethylmethacrylate (PMMA) conversion values measured by gel filtration chromatography.
• PMMA polymethylmethacrylate
• the number average molecular weight of the polyimide obtained by the above-mentioned production method 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 from the same viewpoint.
• the number average molecular weight of the polyamic acid obtained by the above-mentioned production method 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 from the same viewpoint.
• Examples of the compound that gives the structural unit (A1) as the tetracarboxylic acid component used as a raw material in the present production method include, but are not limited to, the compound represented by the formula (a1), as long as the same structural unit is given. It may be the derivative. Examples of the derivative include a tetracarboxylic acid corresponding to the compound represented by the formula (a1) and an alkyl ester of the tetracarboxylic acid. As the compound that gives the structural unit (A1), the compound represented by the formula (a1) is preferable.
• the compound giving the structural unit (A2) includes a 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 is given.
• 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 that gives the structural unit (A2) the compound represented by the formula (a2) is preferable.
• the compound giving the structural unit (A3) includes, but is not limited to, the compound represented by the formula (a3), and may be a derivative thereof as long as the same structural unit is given.
• Examples of the derivative include a tetracarboxylic acid corresponding to the compound represented by the formula (a3) and an alkyl ester of the tetracarboxylic acid.
• the compound that gives the structural unit (A3) the compound represented by the formula (a3) is preferable.
• Examples of the compound that gives a structural unit (B1) as a diamine component used as a raw material in the present production method include diamine, but the compound is not limited to this, and may be a derivative 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).
• the compound that gives the structural unit (B2) includes, but is not limited to, a derivative 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 (B2).
• the compound that gives the structural unit (B3) includes, but is not limited to, a derivative thereof as long as the same structural unit is given.
• the derivative include diisocyanates corresponding to diamines. Diamine is preferable as the compound that gives the structural unit (B3).
• the ratio of the amount of the tetracarboxylic acid component to the diamine component charged in all the steps of producing the copolymer including the steps 1 and 2 is 0.9 for the diamine component with respect to 1 mol of the tetracarboxylic acid component. It is preferably ⁇ 1.1 mol.
• an end-capping agent may be used in addition to the above-mentioned tetracarboxylic acid component and diamine component.
• the terminal encapsulant is preferably used in step 2 when both steps 1 and 2 are performed.
• 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 acid 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 polymer (X) may be any solvent as long as it can dissolve the imide-amidoic acid copolymer to be produced.
• 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-methylcaprolactum, 1,3-dimethylimidazolidinone, tetramethylurea and the like.
• Amide-based solvent lactone-based solvent such as ⁇ -butyrolactone and ⁇ -valerolactone, phosphorus-containing amide-based solvent such as hexamethylphosphoric amide and hexamethylphosphintriamide, and sulfur-containing solvent 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 compound (Y) contained in the polymer composition of the present invention is represented by the following general formula (3).
• R 3 is at least one selected from the group consisting of an alkyl group having 1 to 30 carbon atoms, a phenyl group, an alkoxy group, an acryloyl group, a methacryloyl group, an acryloyloxyethyl group, and a methacryloyloxyethyl group.
• n is 0 to 2.
• R 3 is at least one selected from the group consisting of an alkyl group having 1 to 30 carbon atoms, a phenyl group, an alkoxy group, an acryloyl group, a methacryloyl group, an acryloyloxyethyl group, and a methacryloyloxyethyl group. It is preferably an alkyl group having 1 to 30 carbon atoms.
• the plurality of R 3s may be the same or different, but are preferably the same.
• n is 0 to 2, preferably 1 to 2.
• the compound (Y) is a phosphorus compound, and specific examples of the compound (Y) include at least one selected from the group consisting of an acidic phosphoric acid ester and a phosphoric acid, and an acidic phosphoric acid ester is preferable.
• the acidic phosphoric acid ester include isotridecyl acid phosphate, dibutyl phthalate and the like, and isotridecyl acid phosphate is preferable.
• the content of the compound (Y) is preferably 10 ppm or more and 10,000 ppm or less, more preferably 100 ppm or more and 5,000 ppm or less, and further preferably 500 ppm or more and 2,000 ppm or less with respect to the polymer (X). Is.
• the amount of the compound (Y) is in this range, a film having a low yellowness can be obtained while having heat resistance, and the transparency of the film can be further improved.
• "ppm" indicates parts per million by mass.
• the varnish of the present invention is obtained by dissolving the above-mentioned polymer composition in an organic solvent. That is, the varnish of the present invention is formed by dissolving the polymer (X) and the compound (Y) in an organic solvent, and the varnish of the present invention contains the polymer (X), the compound (Y) and the organic solvent. The polymer (X) and the compound (Y) are dissolved in the organic solvent.
• the organic solvent may be any one that dissolves the polymer (X) and the compound (Y), and is not particularly limited, but the above-mentioned compound may be used alone or in combination of two or more as the solvent used for producing the polymer (X). It is preferable to mix and use.
• the varnish of the present invention may be one in which compound (Y) is mixed and dissolved in the above-mentioned polymer (X) solution, or one in which a diluting solvent is further added.
• the polymer (X) contained in the varnish of the present invention contains a repeating unit (amidoic acid moiety) represented by the formula (2), further imidization is performed from the viewpoint of efficiently advancing the imidization of the amidic acid moiety.
• a catalyst and a dehydration catalyst can be contained.
• 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 will be colored when dried at a high temperature after the film is formed, and the appearance will not be impaired.
• the imidization catalyst has a boiling point of 40 ° C. or higher, the possibility of volatilization before the imidization proceeds sufficiently can be avoided.
• the amine compound preferably used as an imidization catalyst include pyridine and picoline.
• the above imidization catalyst may be used alone or in combination of two or more.
• 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 polymer (X) 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 a fluorescent whitening agent as long as the required characteristics of the polyimide film are not impaired. It may contain various additives such as an agent, a cross-linking agent, a polymerization initiator, and a photosensitizer.
• 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 comprises a polyimide resin obtained by imidizing the amid acid moiety of the polymer (X). Contains compound (Y).
• the polymer (X) is polyimide, it contains the polyimide, a polyimide resin whose molecular weight has been further adjusted by heating, and compound (Y). Therefore, the polyimide film of the present invention has excellent heat resistance and low yellowness.
• the polyimide film of the present invention can be produced by using the above-mentioned varnish.
• the method for producing a polyimide film using the varnish of the present invention is not particularly limited, but the following method is preferable. That is, the method of applying the above-mentioned varnish on the support and heating is preferable, and specifically, the varnish in which the polymer (X) and the compound (Y) are dissolved in an organic solvent is applied on the support. , The method of heating is preferable. Further, as the polyimide film of the present invention, a polyimide film obtained by applying the above-mentioned varnish on a support and heating it is preferable, and specifically, the polymer (X) and the compound (Y) are organic solvents. A polyimide film obtained by applying a varnish dissolved in a varnish on a support and heating it is preferable.
• the support examples include a smooth glass plate, a metal plate, a plastic, and the like.
• the organic solvent such as the reaction solvent and the diluting solvent contained in the varnish is removed by heating to obtain a polymer film, which is then contained in the polymer film.
• the polyimide film can be produced by imidizing (dehydrating and ring-closing) the polymer by heating and then peeling it from the support.
• 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.
• the weight average molecular weight of the copolymer can be obtained from, for example, a standard polymethylmethacrylate (PMMA) conversion value measured by gel filtration chromatography.
• PMMA polymethylmethacrylate
• the heating temperature for drying the varnish of the present invention to obtain a polymer film is preferably 50 to 150 ° C.
• the heating temperature for imidizing the polymer by heating is preferably 200 to 500 ° C, more preferably 250 to 450 ° C, and even more preferably 300 to 430 ° 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 having a gas content of 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 and the like, but is preferably 1 to 250 ⁇ m, more preferably 5 to 100 ⁇ m, and further 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 the viscosity of the varnish.
• the polymer composition of the present invention By using the polymer composition of the present invention, it is possible to obtain a polyimide film having excellent heat resistance, little change in hue after heat treatment, and a low yellowness, and the obtained polyimide film of the present invention has heat resistance. Excellent, little change in hue after heat treatment, and low yellowness.
• the suitable physical property values of the film are as follows.
• the total light transmittance is preferably 84% or more, more preferably 87% or more, and further preferably 90% or more when the film has a thickness of 10 ⁇ m.
• the yellow index (YI) is preferably 16 or less, more preferably 12 or less, and preferably 6 or less, more preferably 4 or less from the viewpoint of excellent colorlessness, when a film having a thickness of 10 ⁇ m is formed. be.
• the 1% weight loss temperature is preferably 430 ° C. or higher, more preferably 480 ° C. or higher, still more preferably 500 ° C. or higher, and even more preferably 510 ° C. or higher.
• the 1% weight loss temperature is the temperature at which the polyimide film is heated to 40 to 550 ° C. at a heating rate of 10 ° C./min and the weight is reduced by 1% as compared with the weight at 300 ° 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.
• film thickness was measured using a micrometer manufactured by Mitutoyo Co., Ltd.
• the film thicknesses of Examples 9 to 10 and Comparative Examples 8 to 9 were measured using a film thickness measuring device Filmtrics F20 (manufactured by Filmometrics Co., Ltd.).
• Total light transmittance, yellow index (YI) Total light transmittance conforms to JIS K7105: 1981, YI conforms to ASTM D1925 (C light source, 2 °), and is measured using a color and turbidity simultaneous measuring instrument "COH7700" manufactured by Nippon Denshoku Industries Co., Ltd. did.
• 1% weight loss temperature (Td1%) A differential thermogravimetric simultaneous measuring device "NEXTA STA200RV" manufactured by Hitachi High-Tech Science Corporation was used. The temperature of the sample was raised to 40 to 150 ° C. at a heating rate of 10 ° C./min, held at 150 ° C. for 30 minutes, and after removing water, the temperature was raised to 550 ° C. The temperature at which the weight was reduced by 1% as compared with the weight after holding at 150 ° C. for 30 minutes was defined as the 1% weight loss temperature. The larger the value, the better the weight reduction temperature.
• the laminated film was prepared as follows.
• the polyimide films obtained in Examples and Comparative Examples were not peeled off, a SiO 2 film having a thickness of 300 nm was formed on the polyimide film by sputtering, and an ITO (indium tin oxide) film having a thickness of 1230 nm was formed on the SiO 2 film.
• Annie ring (heating) was performed for 1 hour.
• the annealing (heating) temperature was 360 ° C. for Examples 1 to 8 and Comparative Examples 1 to 7, and 400 ° C.
• DBP Dibutyl phosphate (manufactured by Johoku Chemical Industry Co., Ltd., a compound in which R 3 is a butyl group and n is 2 in formula (3)).
• Phosphoric acid A compound in which n is 0 in the formula (3) trimethyl phosphate: A compound in which R 3 is a methyl group and n is 3 in the formula (3)
• Triphenylphosphine R in the formula (3)
• Ilganox 1010 antioxidant
• Pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (manufactured by BASF Japan Ltd.)
• BYK-378 Silicone-based surface conditioner (manufactured by Big Chemie Japan Co., Ltd.)
• NMP N-methyl-2-pyrrolidone (manufactured by Tokyo Junyaku Kogyo Co., Ltd.)
• GBL ⁇ -Butyrolactone (manufactured by Mitsubishi Chemical Corporation)
• TEA Triethylamine (manufactured by Kanto Chemical Co., Inc.)
• Example 1 32.024g (0.100mol) of TFMB in a 1L 5-necked round-bottom flask equipped with a stainless half-moon stirring blade, a nitrogen inlet tube, a Dean Stark with a cooling tube, a thermometer, and a glass end cap.
• NMP was added in an amount of 196.627 g, and the mixture was stirred at a system temperature of 50 ° C. and a nitrogen atmosphere at a rotation speed of 150 rpm to obtain a solution.
• 29.422 g (0.100 mol) of s-BPDA and 49.157 g of NMP were collectively added to this solution, and the mixture was stirred with a mantle heater at 50 ° C. for 7 hours.
• 307.230 g of NMP was added, and the mixture was further stirred for about 3 hours to homogenize to obtain a polyamic acid varnish having a solid content concentration of 10.0% by mass.
• Example 1 except that 0.01 g (1000 ppm with respect to polyamic acid) of each of the phosphorus compounds or other compounds shown in Table 1 was used instead of 0.01 g (1000 ppm with respect to polyamic acid) of JP-513.
• a polyimide film was obtained by the same method as in the above. The results are shown in Table 1.
• Example 4 26.644 g (0.083 mol) of TFMB in a 1 L 5-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.
• 3,5-DABA (3.165 g (0.021 mol)) and GBL (163.792 g) were added, and the mixture was stirred at a system temperature of 70 ° C. and a nitrogen atmosphere at a rotation speed of 150 rpm to obtain a solution.
• Examples 5 and 6 The same method as in Example 4 except that 0.01 g (1000 ppm with respect to polyamic acid) of each of the phosphorus compounds shown in Table 1 was used instead of 0.01 g (1000 ppm with respect to polyamic acid) of JP-513. To obtain a polyimide film. The results are shown in Table 1.
• Example 7 25.619 g (0.080 mol) of TFMB in a 1 L 5-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.
• 3,5-DABA (3.043 g (0.020 mol)) and GBL (156.713 g) were added, and the mixture was stirred at a system temperature of 70 ° C. and a nitrogen atmosphere at a rotation speed of 150 rpm to obtain a solution.
• Example 8 32.024g (0.100mol) of TFMB in a 1L 5-necked round-bottom flask equipped with a stainless half-moon stirring blade, a nitrogen inlet tube, a Dean Stark with a cooling tube, a thermometer, and a glass end cap. And 169.109 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 150 rpm to obtain a solution.
• Example 8 A polyimide film was obtained by the same method as in Example 9 except that JP-513 was not used. The results are shown in Table 1. Since the polyimide film obtained in Comparative Example 8 could not be peeled off from the glass plate, the total light transmittance and the yellow index (YI) of Example 9 and Comparative Example 8 were measured including the glass plate. Further, for the polyimide film obtained in Comparative Example 8, the 1% weight loss temperature (Td1%) was not measured.
• ⁇ Comparative Example 9> A polyimide film was obtained by the same method as in Example 10 except that JP-513 was not used. The results are shown in Table 1. Since the polyimide film obtained in Comparative Example 9 could not be peeled off from the glass plate, the total light transmittance and the yellow index (YI) of Examples 10 and 9 were measured including the glass plate. Further, for the polyimide film obtained in Comparative Example 9, the 1% weight loss temperature (Td1%) was not measured.
• the polyimide film obtained from the polymer composition of the present invention is excellent in heat resistance and colorlessness after heat treatment, and has a low yellowness. Further, it can be seen that the polyimide film of the example is also excellent in transparency as compared with the polyimide film of the corresponding comparative example.

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• 2021
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