CN111164131B - Imide resin, polyimide varnish, and polyimide film - Google Patents

Imide resin, polyimide varnish, and polyimide film Download PDF

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CN111164131B
CN111164131B CN201880064165.1A CN201880064165A CN111164131B CN 111164131 B CN111164131 B CN 111164131B CN 201880064165 A CN201880064165 A CN 201880064165A CN 111164131 B CN111164131 B CN 111164131B
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CN111164131A (en
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安孙子洋平
村山智寿
冈田佳奈
关口慎司
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Mitsubishi Gas Chemical Co Inc
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    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1042—Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds
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    • 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
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • 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
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    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1057—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain
    • C08G73/106—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain containing silicon
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    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1057—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain
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    • C09J179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
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    • 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

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Abstract

A polyimide resin comprising a structural unit A derived from a tetracarboxylic dianhydride and a structural unit B derived from a diamine, the structural unit A comprising a structural unit (A-1) derived from a compound represented by the following formula (a-1) and a structural unit (A-2) derived from a compound represented by the following formula (a-2), and the structural unit B comprising a structural unit (B-1) derived from a compound represented by the following formula (B-1). (in the formula (b-1), R is each independently a hydrogen atom, a fluorine atom or a methyl group).

Description

Imide resin, polyimide varnish, and polyimide film
Technical Field
The present invention relates to a polyimide resin, a polyimide varnish, and a polyimide film.
Background
In recent years, with the advent of a high-level information society, materials having both heat resistance and colorless transparency have been required in the fields of optical communications such as optical fibers and optical waveguides, and in the fields of display devices such as liquid crystal alignment films and color filters.
In the field of display devices, in order to reduce the weight and flexibility of devices, replacement of glass substrates used in the devices with plastic substrates that can reduce the weight and flexibility has been studied. In the case where light emitted from the display element is emitted through the plastic substrate, the plastic substrate is required to have colorless transparency, and when light passes through the retardation film or the polarizing plate (for example, a liquid crystal display, a touch panel, or the like), high optical isotropy is required in addition to the colorless transparency.
As a plastic material that can satisfy the above-described requirements, development of polyimide resins has been advanced. For example, patent document 1 discloses a polyimide resin or the like synthesized using 1,2,4, 5-cyclohexanetetracarboxylic dianhydride as a tetracarboxylic acid component and 9, 9-bis (3-methyl-4-aminophenyl) fluorene and 4, 4' -diaminodiphenyl ether as diamine components, as a polyimide resin having excellent transparency, heat resistance and optical isotropy.
In recent years, in the field of microelectronics, laser lift-off processing called laser lift-off (LLO) has been attracting attention as a method for separating a support laminated with a resin film from the resin film. Therefore, in order to make the polyimide film compatible with laser peeling processing, the polyimide film is also required to have laser peelability. In order to cope with the peeling processing by an XeCl excimer laser at a wavelength of 308nm, the polyimide film is required to have excellent characteristics of absorbing light at the wavelength of 308nm (i.e., small light transmittance at the wavelength of 308 nm).
Documents of the prior art
Patent document
Patent document 1: japanese patent No. 6010533
Disclosure of Invention
Problems to be solved by the invention
The present invention has been made in view of the above circumstances, and an object thereof is to provide a polyimide resin having excellent colorless transparency, optical isotropy, and laser peelability.
Means for solving the problems
The present inventors have found that a polyimide resin containing a combination of specific structural units can solve the above problems, and have completed the present invention.
That is, the present invention relates to the following [1] to [8 ].
[1] A polyimide resin comprising: a structural unit A derived from a tetracarboxylic dianhydride and a structural unit B derived from a diamine,
the structural unit A comprises a structural unit (A-1) derived from a compound represented by the following formula (a-1) and a structural unit (A-2) derived from a compound represented by the following formula (a-2),
the structural unit B contains a structural unit (B-1) derived from a compound represented by the following formula (B-1).
Figure BDA0002434705300000021
(in the formula (b-1), R is each independently a hydrogen atom, a fluorine atom or a methyl group.)
[2] The polyimide resin according to the above [1], wherein the ratio of the structural unit (A-1) in the structural unit A is 10 to 90 mol%,
the proportion of the structural unit (A-2) in the structural unit A is 10 to 90 mol%.
[3] The polyimide resin according to the above [1] or [2], wherein the proportion of the structural unit (B-1) in the structural unit B is 30 to 100 mol%.
[4] The polyimide resin according to any one of the above [1] to [3], wherein the structural unit B further comprises at least 1 structural unit (B-2) selected from the group consisting of a structural unit (B-2-1) derived from a compound represented by the following formula (B-2-1), a structural unit (B-2-2) derived from a compound represented by the following formula (B-2-2), and a structural unit (B-2-3) derived from a compound represented by the following formula (B-2-3).
Figure BDA0002434705300000031
(in the formula (b-2-3),
R 1 ～R 4 each independently a monovalent aliphatic group or a monovalent aromatic group,
Z 1 and Z 2 Each independently a divalent aliphatic group or a divalent aromatic group,
r is a positive integer. )
[5] The polyimide resin according to the above [4], wherein the ratio of the structural unit (B-1) in the structural unit B is 30 to 95 mol%,
the proportion of the structural unit (B-2) in the structural unit B is 5 to 70 mol%.
[6] The polyimide resin according to any one of the above [1] to [5], wherein R represents a hydrogen atom.
[7] A polyimide varnish obtained by dissolving the polyimide resin according to any one of the above [1] to [6] in an organic solvent.
[8] A polyimide film comprising the polyimide resin according to any one of the above [1] to [6 ].
ADVANTAGEOUS EFFECTS OF INVENTION
The polyimide resin of the present invention is excellent in colorless transparency, optical isotropy and laser peelability.
Detailed Description
[ polyimide resin ]
The polyimide resin of the present invention comprises a structural unit A derived from a tetracarboxylic dianhydride and a structural unit B derived from a diamine, the structural unit A comprises a structural unit (A-1) derived from a compound represented by the following formula (a-1) and a structural unit (A-2) derived from a compound represented by the following formula (a-2), and the structural unit B comprises a structural unit (B-1) derived from a compound represented by the following formula (B-1).
Figure BDA0002434705300000041
(in the formula (b-1), R is each independently a hydrogen atom, a fluorine atom or a methyl group.)
< structural unit A >)
The structural unit A is a structural unit derived from a tetracarboxylic dianhydride, and comprises a structural unit (A-1) derived from a compound represented by the formula (a-1) and a structural unit (A-2) derived from a compound represented by the formula (a-2). The structural unit (A-1) improves the colorless transparency, and the structural unit (A-2) improves the heat resistance, optical isotropy and laser peelability.
The compound represented by the formula (a-1) is 1,2,4, 5-cyclohexanetetracarboxylic dianhydride.
The compound represented by the formula (a-2) is 9, 9' -bis (3, 4-dicarboxyphenyl) fluorene dianhydride.
The proportion of the structural unit (A-1) in the structural unit A is preferably 10 to 90 mol%, more preferably 25 to 75 mol%, and still more preferably 40 to 60 mol%.
The proportion of the structural unit (a-2) in the structural unit a is preferably 10 to 90 mol%, more preferably 25 to 75 mol%, and still more preferably 40 to 60 mol%.
The total content ratio of the structural unit (A-1) and the structural unit (A-2) in the structural unit A is preferably 20 mol% or more, more preferably 50 mol% or more, and still more preferably 80 mol% or more. The upper limit of the total content ratio of the structural unit (A-1) and the structural unit (A-2) is not particularly limited, that is, 100 mol%. The structural unit A may be composed of only the structural unit (A-1) and the structural unit (A-2).
The structural unit A may contain structural units other than the structural units (A-1) and (A-2). The tetracarboxylic dianhydride forming such a structural unit is not particularly limited, and examples thereof include: aromatic tetracarboxylic dianhydrides such as pyromellitic dianhydride, 3 ', 4,4 ' -biphenyltetracarboxylic dianhydride, and 4,4 ' - (hexafluoroisopropylidene) diphthalic anhydride (except for the compound represented by the formula (a-2)); alicyclic tetracarboxylic dianhydrides such as 1,2,3, 4-cyclobutanetetracarboxylic dianhydride, norbornane-2-spiro- α -cyclopentanone- α' -spiro-2 ″ -norbornane-5, 5 ″,6,6 ″ -tetracarboxylic dianhydride (except for the compound represented by formula (a-1)); and aliphatic tetracarboxylic acid dianhydrides such as 1,2,3, 4-butanetetracarboxylic acid dianhydride.
In the present specification, an aromatic tetracarboxylic dianhydride refers to a tetracarboxylic dianhydride containing 1 or more aromatic rings, an alicyclic tetracarboxylic dianhydride refers to a tetracarboxylic dianhydride containing 1 or more alicyclic rings and no aromatic rings, and an aliphatic tetracarboxylic dianhydride refers to a tetracarboxylic dianhydride containing no aromatic rings and no alicyclic rings.
The structural units arbitrarily contained in the structural unit A, that is, the structural units other than the structural units (A-1) and (A-2), may be 1 kind or 2 or more kinds.
< structural unit B >
The structural unit B is a diamine-derived structural unit comprising the structural unit (B-1) derived from the compound represented by the formula (B-1). The structural unit (B-1) improves heat resistance, optical isotropy and laser peelability.
In the formula (b-1), each R is independently selected from the group consisting of a hydrogen atom, a fluorine atom and a methyl group, and is preferably a hydrogen atom. Examples of the compound represented by the formula (b-1) include 9, 9-bis (4-aminophenyl) fluorene, 9-bis (3-fluoro-4-aminophenyl) fluorene and 9, 9-bis (3-methyl-4-aminophenyl) fluorene, and 9, 9-bis (4-aminophenyl) fluorene is preferable.
The proportion of the structural unit (B-1) in the structural unit B is preferably 30 to 100 mol%, more preferably 30 to 95 mol%, and still more preferably 40 to 90 mol%. The structural unit B may be composed of only the structural unit (B-1).
The structural unit B may contain a structural unit other than the structural unit (B-1), and preferably further contains a structural unit (B-2), and the structural unit (B-2) is at least 1 selected from the group consisting of a structural unit (B-2-1) derived from a compound represented by the following formula (B-2-1), a structural unit (B-2-2) derived from a compound represented by the following formula (B-2-2), and a structural unit (B-2-3) derived from a compound represented by the following formula (B-2-3).
Figure BDA0002434705300000061
(in the formula (b-2-3),
R 1 ～R 4 each independently a monovalent aliphatic group or a monovalent aromatic group,
Z 1 and Z 2 Each independently a divalent aliphatic group or a divalent aromatic group,
r is a positive integer. )
The compound represented by the formula (b-2-1) is bis (4-aminophenyl) sulfone.
The compound represented by the formula (b-2-2) is 2, 2' -bis (trifluoromethyl) benzidine.
R in the formula (b-2-3) 1 、R 2 、R 3 And R 4 Each independently represents a monovalent aliphatic group or a monovalent aromatic group, which may be substituted with a fluorine atom. Examples of the monovalent aliphatic group include a monovalent saturated hydrocarbon group and a monovalent unsaturated hydrocarbon group. The monovalent saturated hydrocarbon group includes an alkyl group having 1 to 22 carbon atoms, and examples thereof include a methyl group, an ethyl group, and a propyl group. The monovalent unsaturated hydrocarbon group includes an alkenyl group having 2 to 22 carbon atoms, and examples thereof include an ethenyl group and an propenyl group. Examples of the monovalent aromatic group include aryl groups having 6 to 24 carbon atoms and aralkyl groups. As R 1 、R 2 、R 3 And R 4 Particularly preferred is a methyl group or a phenyl group.
In addition, Z 1 And Z 2 Each independently represents a divalent aliphatic group or a divalent aromatic group, which may be substituted with a fluorine atom. The divalent aliphatic group may be a divalent saturated hydrocarbon group or a divalent unsaturated hydrocarbon group. The divalent saturated hydrocarbon group includes an alkylene group having 1 to 22 carbon atoms, and examples thereof include a methylene group, an ethylene group, and a propylene group. The divalent unsaturated hydrocarbon group includes unsaturated hydrocarbon groups having 2 to 22 carbon atoms, and examples thereof include an ethenylene group, an propenylene group, and an alkylene group having an unsaturated double bond at a terminal. Examples of the divalent aromatic group include a phenylene group having 6 to 24 carbon atoms, a phenylene group substituted with an alkyl group, and an aralkylene group. As Z 1 And Z 2 Propylene, phenylene and aralkylene are particularly preferable.
R represents a positive integer, preferably an integer of 10 to 10000.
As commercially available compounds that can be obtained AS compounds represented by the formula (B-2-3), "X-22-9409", "X-22-1660B", "X-22-161 AS", "X-22-161A" and "X-22-161B" manufactured by shin-Etsu chemical Co., Ltd.
The structural unit (B-2-1) is preferable from the viewpoint of improving colorless transparency. The structural unit (B-2-2) is preferable from the viewpoint of improving colorless transparency and from the viewpoint of imparting low water absorption. The structural unit (B-2-3) is preferable from the viewpoint of imparting optical isotropy and low water absorption. The polyimide resin having low water absorption has good dimensional stability in moisture absorption.
When the structural unit B comprises the structural unit (B-1) and the structural unit (B-2), the ratio of the structural unit (B-1) in the structural unit B is preferably 30 to 95 mol%, more preferably 40 to 90 mol%, and the ratio of the structural unit (B-2) in the structural unit B is preferably 5 to 70 mol%, more preferably 10 to 60 mol%.
The total content ratio of the structural unit (B-1) and the structural unit (B-2) in the structural unit B is preferably 35 mol% or more, and more preferably 50 mol% or more. The upper limit of the total content ratio of the structural unit (B-1) and the structural unit (B-2) is not particularly limited, i.e., 100 mol%. The structural unit B may be composed of only the structural unit (B-1) and the structural unit (B-2).
The structural unit (B-2) may be only the structural unit (B-2-1), may be only the structural unit (B-2-2), or may also be only the structural unit (B-2-3).
Further, the structural unit (B-2) may be a combination of the structural unit (B-2-1) and the structural unit (B-2-2), may be a combination of the structural unit (B-2-2) and the structural unit (B-2-3), or may also be a combination of the structural unit (B-2-1) and the structural unit (B-2-3).
Further, the structural unit (B-2) may be a combination of the structural unit (B-2-1) and the structural unit (B-2-2) and the structural unit (B-2-3).
The constitutional unit arbitrarily contained in the constitutional unit B (i.e., the constitutional unit other than the constitutional unit (B-1)) is not limited to the constitutional unit (B-2) described above. The diamine forming such an arbitrary structural unit is not particularly limited, and examples thereof include 1, 4-phenylenediamine, p-xylylenediamine, 3, 5-diaminobenzoic acid, 2 ' -dimethylbiphenyl-4, 4 ' -diamine, 4 ' -diaminodiphenyl ether, 4 ' -diaminodiphenylmethane, 2-bis (4-aminophenyl) hexafluoropropane, 4 ' -diaminobenzanilide, 1- (4-aminophenyl) -2, 3-dihydro-1, 3, 3-trimethyl-1H-indene-5-amine, α ' -bis (4-aminophenyl) -1, 4-diisopropylbenzene, N ' -bis (4-aminophenyl) terephthalamide, N-bis (4-aminophenyl) terephthalamide, and the like, Aromatic diamines such as 4, 4' -bis (4-aminophenoxy) biphenyl, 2-bis [ 4- (4-aminophenoxy) phenyl ] propane and 2, 2-bis (4- (4-aminophenoxy) phenyl) hexafluoropropane (except for the compound represented by the formula (b-1), the compound represented by the formula (b-2-2) and the compound represented by the formula (b-2-3)); alicyclic diamines such as 1, 3-bis (aminomethyl) cyclohexane and 1, 4-bis (aminomethyl) cyclohexane; and aliphatic diamines such as ethylenediamine and hexamethylenediamine (except for the compound represented by the formula (b-2-3)).
In the present specification, an aromatic diamine refers to a diamine containing 1 or more aromatic rings, an alicyclic diamine refers to a diamine containing 1 or more alicyclic rings and no aromatic rings, and an aliphatic diamine refers to a diamine containing no aromatic rings and no alicyclic rings.
The structural unit(s) optionally contained in the structural unit(s) B (i.e., structural units other than (B-1)) may be 1 or 2 or more.
The polyimide resin of the present invention preferably has a number average molecular weight of 5000 to 100000 from the viewpoint of mechanical strength of the polyimide film to be obtained. The number average molecular weight of the polyimide resin can be determined, for example, by a standard polymethyl methacrylate (PMMA) conversion value measured by gel filtration chromatography.
The polyimide resin of the present invention is excellent in colorless transparency, optical isotropy, and laser peelability, and therefore 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 86% or more, further preferably 87% or more, and particularly preferably 88% or more, when formed into a polyimide film having a thickness of 10 μm.
The polyimide resin of the present invention has a Yellowness Index (YI) of preferably 3.0 or less, more preferably 2.4 or less, still more preferably 2.0 or less, and particularly preferably 1.8 or less when formed into a polyimide film having a thickness of 10 μm.
The absolute value of retardation (Rth) in thickness of the polyimide resin of the present invention is preferably 100nm or less, more preferably 85nm or less, further preferably 60nm or less, and particularly preferably 45nm or less when a polyimide film having a thickness of 10 μm is formed.
The polyimide resin of the present invention has a light transmittance at a wavelength of 308nm of preferably 1.0% or less, more preferably 0.8% or less, even more preferably 0.5% or less, and particularly preferably 0.3% or less, when a polyimide film having a thickness of 10 μm is formed. The smaller the light transmittance at a wavelength of 308nm, the more excellent the laser peelability at a wavelength of 308nm based on the XeCl excimer laser.
The total linear light transmittance, the Yellow Index (YI), the retardation in thickness (Rth), and the light transmittance at a wavelength of 308nm in the present invention can be measured specifically by the methods described in examples.
In addition, the polyimide resin according to one embodiment of the present invention has low water absorption. Therefore, the water absorption is preferably 2.5% or less, more preferably 2.0% or less, still more preferably 1.5% or less, and particularly preferably 1.2% or less.
The water absorption in the present invention can be measured specifically by the method described in examples.
[ Process for producing polyimide resin ]
The polyimide resin of the present invention can be produced by reacting a tetracarboxylic acid component containing a compound having the structural unit (A-1) and a compound having the structural unit (A-2) with a diamine component; the diamine component contains a compound that imparts the structural unit (B-1) described above.
The compound to be added to the structural unit (A-1) is not limited to the compound represented by the formula (a-1), and may be a derivative thereof insofar as the same structural unit can be formed. Examples of the derivative include a tetracarboxylic acid corresponding to the tetracarboxylic dianhydride represented by the formula (a-1) (i.e., 1,2,4, 5-cyclohexanetetracarboxylic acid) and an alkyl ester of the tetracarboxylic acid. As the compound to be added to the structural unit (A-1), a compound represented by the formula (a-1) (i.e., dianhydride) is preferable.
The compound to which the structural unit (A-2) is added may be a compound represented by the formula (a-2), but is not limited thereto, and may be a derivative thereof insofar as the same structural unit can be formed. Examples of the derivative include a tetracarboxylic acid corresponding to the tetracarboxylic dianhydride represented by the formula (a-2) and an alkyl ester of the tetracarboxylic acid. As the compound to be added to the structural unit (A-2), a compound represented by the formula (a-2) (i.e., dianhydride) is preferable.
The compound to which the structural unit (B-1) is added may be a compound represented by the formula (B-1), but is not limited thereto, and may be a derivative thereof insofar as the same structural unit can be formed. As the derivative, a diisocyanate corresponding to the diamine represented by the formula (b-1) can be mentioned. As the compound to which the structural unit (B-1) is imparted, a compound represented by the formula (B-1) (i.e., diamine) is preferable.
The tetracarboxylic acid component preferably contains 10 to 90 mol%, more preferably 25 to 75 mol%, and still more preferably 40 to 60 mol% of a compound that imparts the structural unit (a-1).
The tetracarboxylic acid component preferably contains 10 to 90 mol%, more preferably 25 to 75 mol%, and still more preferably 40 to 60 mol% of a compound that imparts the structural unit (a-2).
The tetracarboxylic acid component preferably contains 20 mol% or more, more preferably 50 mol% or more, and still more preferably 80 mol% or more of the compound that imparts the structural unit (A-1) and the compound that imparts the structural unit (A-2) in total. The upper limit of the total content ratio of the compound having the structural unit (A-1) and the compound having the structural unit (A-2) is not particularly limited, that is, 100 mol%. The tetracarboxylic acid component may be composed of only the compound having the structural unit (A-1) and the compound having the structural unit (A-2).
The tetracarboxylic acid component may contain compounds other than the compound that provides the structural unit (a-1) and the compound that provides the structural unit (a-2), and examples of the compounds include the above-mentioned aromatic tetracarboxylic acid dianhydride, alicyclic tetracarboxylic acid dianhydride, and aliphatic tetracarboxylic acid dianhydride, and derivatives thereof (e.g., tetracarboxylic acid, alkyl ester of tetracarboxylic acid).
The compound (i.e., a compound other than the compound providing the structural unit (A-1) and the compound providing the structural unit (A-2)) optionally contained in the tetracarboxylic acid component may be 1 or 2 or more.
The diamine component preferably contains 30 to 100 mol%, more preferably 30 to 95 mol%, and still more preferably 40 to 90 mol% of a compound that imparts the structural unit (B-1). The diamine component may be composed of only the compound that provides the structural unit (B-1).
The diamine component may contain a compound other than the compound imparting the structural unit (B-1), and preferably further contains a compound imparting the structural unit (B-2).
Examples of the compound to which the structural unit (B-2) is added include a compound represented by the formula (B-2-1), a compound represented by the formula (B-2-2), and a compound represented by the formula (B-2-3), but the compound is not limited thereto, and derivatives thereof may be included as long as the same structural unit can be formed. Examples of the derivative include diisocyanates corresponding to diamines represented by the formulae (b-2-1) to (b-2-3). As the compound to which the structural unit (B-2) is added, compounds represented by the formulae (B-2-1) to (B-2-3) (i.e., diamines) are preferable.
When the diamine component contains a compound that provides the structural unit (B-1) and a compound that provides the structural unit (B-2), the diamine component preferably contains 30 to 95 mol%, more preferably 40 to 90 mol%, of the compound that provides the structural unit (B-1), and preferably contains 5 to 70 mol%, more preferably 10 to 60 mol%, of the compound that provides the structural unit (B-2).
The diamine component preferably contains 35 mol% or more, more preferably 50 mol% or more of the compound having the structural unit (B-1) and the compound having the structural unit (B-2) in total. The upper limit of the total content ratio of the compound having the structural unit (B-1) and the compound having the structural unit (B-2) is not particularly limited, that is, 100 mol%. The diamine component may be composed of only the compound having the structural unit (B-1) and the compound having the structural unit (B-2).
The compound optionally contained in the diamine component (i.e., the compound other than the compound providing the structural unit (B-1)) is not limited to the compound providing the structural unit (B-2). Examples of such optional compounds include the above-mentioned aromatic diamine, alicyclic diamine, and aliphatic diamine, and derivatives thereof (e.g., diisocyanate).
The number of the compounds optionally contained in the diamine component (i.e., compounds other than the compound providing the structural unit (B-1)) may be 1 or 2 or more.
In the present invention, the ratio of the amount of the tetracarboxylic acid component and the diamine component added to produce the polyimide resin is preferably 0.9 to 1.1 mol per 1 mol of the diamine component in the tetracarboxylic acid component.
In the present invention, in the production of the polyimide resin, an end-capping agent may be used in addition to the tetracarboxylic acid component and the diamine component. As the end-capping agent, monoamines or dicarboxylic acids are preferred. The amount of the end-capping agent to be introduced is preferably 0.0001 to 0.1 mol, and particularly preferably 0.001 to 0.06 mol, based on 1 mol of the tetracarboxylic acid component. As the monoamine-type blocking agent, for example, 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 suitably used. As the dicarboxylic acid-based end capping agent, dicarboxylic acids are preferred, and a part of the ring may be closed. For example, 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. Among these, phthalic acid and phthalic anhydride can be suitably used.
The method for reacting the tetracarboxylic acid component with the diamine component is not particularly limited, and a known method can be used.
Specific examples of the reaction method include the following methods: (1) a method of adding a tetracarboxylic acid component, a diamine component and a reaction solvent into a reactor, stirring at room temperature to 80 ℃ for 0.5 to 30 hours, and then heating and carrying out an imidization reaction; (2) a method in which a diamine component and a reaction solvent are put into a reactor to be dissolved, and then a tetracarboxylic acid component is put into the reactor, and the mixture is stirred at room temperature to 80 ℃ for 0.5 to 30 hours as required, and then heated to carry out imidization; (3) a method in which a tetracarboxylic acid component, a diamine component and a reaction solvent are charged into a reactor, and the temperature is immediately raised to effect imidization.
The reaction solvent used for producing the polyimide resin may be any solvent which can dissolve the polyimide produced without inhibiting the imidization reaction. Examples thereof include aprotic solvents, phenol solvents, ether solvents, carbonate solvents and the like.
Specific examples of the aprotic solvent include amide solvents such as N, N-dimethylformamide, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam, 1, 3-dimethylimidazolidinone, and tetramethylurea, lactone solvents such as γ -butyrolactone and γ -valerolactone, phosphorus-containing amide solvents such as hexamethylphosphoramide and hexamethylphosphinotriamide, sulfur-containing solvents such as dimethylsulfone, dimethylsulfoxide, and sulfolane, ketone solvents such as acetone, cyclohexanone, and methylcyclohexanone, amine solvents such as picoline and pyridine, and ester solvents such as 2-methoxy-1-methylethyl) acetate.
Specific examples of the phenol solvent include phenol, o-cresol, m-cresol, p-cresol, 2, 3-xylenol, 2, 4-xylenol, 2, 5-xylenol, 2, 6-xylenol, 3, 4-xylenol, and 3, 5-xylenol.
Specific examples of the ether solvent include 1, 2-dimethoxyethane, bis (2-methoxyethyl) ether, 1, 2-bis (2-methoxyethoxy) ethane, bis [ 2- (2-methoxyethoxy) ethyl ] ether, tetrahydrofuran, and 1, 4-dioxane.
Specific examples of the carbonate-based solvent include diethyl carbonate, methylethyl carbonate, ethylene carbonate, and propylene carbonate.
Among the above reaction solvents, an amide solvent or a lactone solvent is preferable. The reaction solvents may be used alone or in combination of two or more.
In the imidization reaction, it is preferable to use a dean-Stark trap or the like, and the reaction is carried out while removing the water produced during the production. By performing such an operation, the degree of polymerization and the imidization ratio can be further increased.
The imidization reaction may use a known imidization catalyst. Examples of the imidization catalyst include a basic catalyst and an acid catalyst.
Examples of the basic catalyst include organic basic catalysts such as pyridine, quinoline, isoquinoline, α -picoline, β -picoline, 2, 4-lutidine, 2, 6-lutidine, trimethylamine, triethylamine, tripropylamine, tributylamine, triethylenediamine, imidazole, N-dimethylaniline and N, N-diethylaniline, and inorganic basic catalysts such as potassium hydroxide, sodium hydroxide, potassium carbonate, sodium carbonate, potassium hydrogen carbonate and sodium hydrogen carbonate.
Examples of the acid catalyst include crotonic acid, acrylic acid, trans-3-hexanoic acid, cinnamic acid, benzoic acid, methylbenzoic acid, o-hydroxybenzoic acid, terephthalic acid, benzenesulfonic acid, p-toluenesulfonic acid, and naphthalenesulfonic acid. The above-mentioned imidization catalyst may be used alone or in combination of two or more.
Among the above, from the viewpoint of handling properties, a basic catalyst is preferably used, an organic basic catalyst is more preferably used, triethylamine is further preferably used, and triethylamine and triethylenediamine are particularly preferably used in combination.
The temperature of the imidization reaction is preferably 120 to 250 ℃ and more preferably 160 to 200 ℃ from the viewpoints of the reaction rate, the suppression of gelation, and the like. The reaction time is preferably 0.5 to 10 hours after the start of distillation to produce water.
[ polyimide varnish ]
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 comprises the polyimide resin of the present invention and an organic solvent in which the polyimide resin is dissolved.
The organic solvent is not particularly limited as long as it dissolves the polyimide resin, and as a reaction solvent for producing the polyimide resin, two or more of the above-mentioned compounds are preferably used alone or in combination.
The polyimide resin of the present invention has solvent solubility, and therefore can be used as a varnish having a high concentration and being stable at room temperature. The polyimide varnish of the present invention preferably contains 5 to 40% by mass, more preferably 10 to 30% by mass of the polyimide resin of the present invention. The viscosity of the polyimide varnish is preferably 1 to 200 pas, more preferably 5 to 150 pas.
The polyimide varnish of the present invention may contain various additives such as inorganic fillers, adhesion promoters, release agents, flame retardants, ultraviolet stabilizers, surfactants, leveling agents, defoaming agents, fluorescent whitening agents, crosslinking agents, polymerization initiators, and photosensitizers, as long as the required properties of the polyimide film are not impaired.
The method for producing the polyimide varnish of the present invention is not particularly limited, and a known method can be used.
[ polyimide film ]
The polyimide film of the present invention comprises the polyimide resin of the present invention. Therefore, the polyimide film of the present invention is excellent in colorless transparency, optical isotropy and laser peelability.
The method for producing the polyimide film of the present invention is not particularly limited, and a known method can be used. For example, a method of applying or molding the polyimide varnish of the present invention in a film form and then removing the organic solvent may be mentioned.
The polyimide film of the present invention is excellent in colorless transparency, optical isotropy and laser peelability, and therefore can be suitably used as a film for various members such as color filters, flexible displays, semiconductor components and optical members. The polyimide film of the present invention can be particularly suitably used as a substrate for an image display device such as a liquid crystal display, an OLED display, or the like.
Examples
The present invention will be described in detail with reference to examples. The present invention is not limited to these examples.
The solid content concentration of the polyimide varnish obtained in the examples and comparative examples and the physical properties of the polyimide film were measured by the following methods.
(1) Concentration of solid component
For the measurement of the solid content concentration of the polyimide varnish, a sample was heated at 320 ℃ for 120 minutes by a small electric furnace "MMF-1" manufactured by AS ONE Corporation, and the measurement was calculated based on the mass difference between the sample before and after heating.
(2) Thickness of film
The film thickness was measured using a micrometer manufactured by Mitutoyo Corporation.
(3) Total light transmittance, Yellow Index (YI)
According to JIS K7361-1, the measurement was carried out using a color/turbidity simultaneous measurement apparatus "COH 400" manufactured by Nippon Denshoku industries Co., Ltd.
(4) Thickness retardation (Rth)
The thickness retardation (Rth) was measured using an ellipsometer "M-220" manufactured by Nippon spectral Co., Ltd. The thickness phase difference was measured at a measurement wavelength of 590 nm. When nx is the maximum value, ny is the minimum value, nz is the refractive index in the thickness direction, and d is the thickness of the film, among the in-plane refractive indices of the polyimide film, Rth is expressed by the following formula.
Rth＝[{(nx+ny)/2}-nz]×d
(5) Light transmittance at wavelength of 308nm
The measurement was carried out using an ultraviolet-visible near infrared spectrophotometer "UV-3100 PC" manufactured by Shimadzu corporation.
(6) Water absorption rate
Determined according to JIS K7209. After drying a polyimide film of 50 mm. times.50 mm at 50 ℃ for 24 hours, the film was returned to room temperature by a dryer, and the weight was measured at 23 ℃ under a humidity of 50. + -. 5% (W0). Subsequently, the film was immersed in distilled water at 23 ℃ for 24 hours, and the surface was wiped off to remove water, and then the weight after 1 minute was measured (W1). The water absorption was calculated based on the following formula.
Water absorption (%) [ (W1-W0)/W0] × 100
< example 1 >
Into a 500mL 5-neck round-bottomed flask equipped with a stainless steel half-moon-shaped stirring blade, a nitrogen introduction tube, a dean-stark trap equipped with a cooling tube, a thermometer, and a glass end cap, 34.845g (0.100 mol) of 9, 9-bis (4-aminophenyl) fluorene (manufactured by Taoka Chemical co., ltd.) and 83.018g of γ -butyrolactone (manufactured by mitsubishi Chemical corporation) were charged, and the mixture was stirred at a system internal temperature of 70 ℃ and a nitrogen atmosphere at a rotation speed of 200rpm to obtain a solution.
To this solution, 11.209g (0.050 mol) of 1,2,4, 5-cyclohexanetetracarboxylic dianhydride (manufactured by Mitsubishi gas Chemical Co., Ltd.), 22.922g (0.050 mol) of 9, 9' -bis (3, 4-dicarboxyphenyl) fluorene dianhydride (manufactured by JFE Chemical Corporation) and 20.755g of γ -butyrolactone (manufactured by Mitsubishi Chemical Co., Ltd.) were added at once, and 5.060g of triethylamine (manufactured by Kanto Chemical Co., Ltd.) and 0.561g of triethylenediamine (manufactured by Tokyo Chemical Co., Ltd.) as an imidization catalyst were added, and heating was performed by a jacketed resistance heater for about 20 minutes to raise the internal temperature of the reaction system to 190 ℃. The distilled components were collected, and the reaction system was refluxed for 5 hours while maintaining the internal temperature of the reaction system at 190 ℃ while adjusting the rotation speed in accordance with the increase in viscosity.
Then, 158.54g of gamma-butyrolactone (manufactured by Mitsubishi chemical corporation) was added, the internal temperature of the reaction system was cooled to 120 ℃, and the mixture was stirred for about 3 hours to be homogenized, thereby obtaining a polyimide varnish having a solid content of 20 mass%. The polyimide varnish thus obtained was coated on a glass plate, and the plate was kept at 80 ℃ for 20 minutes, and then heated at 300 ℃ for 30 minutes in a hot air dryer under a nitrogen atmosphere to evaporate the solvent, thereby obtaining a film having a thickness of 14 μm. The results are shown in Table 1.
< example 2 >
A polyimide varnish was prepared in the same manner as in example 1 except that the amount of 9, 9-bis (4-aminophenyl) fluorene (manufactured by Taoka Chemical co., ltd. was changed from 34.845g (0.100 mol) to 17.423g (0.050 mol), and 12.415g (0.050 mol) of bis (4-aminophenyl) sulfone (manufactured by singham specialty chemicals ltd.) was added, thereby obtaining a polyimide varnish having a solid content of 20 mass%. Using the obtained polyimide varnish, a film was produced in the same manner as in example 1 to obtain a film having a thickness of 10 μm. The results are shown in Table 1.
< example 3 >
A polyimide varnish was prepared in the same manner as in example 2 except that 12.415g (0.050 mol) of bis (4-aminophenyl) sulfone (manufactured by singapon industries, ltd.) was changed to 16.012g (0.050 mol) of 2, 2' -bis (trifluoromethyl) benzidine (manufactured by singapon industries, ltd.) to obtain a polyimide varnish having a solid content of 20 mass%. Using the obtained polyimide varnish, a film was produced in the same manner as in example 1 to obtain a film having a thickness of 12 μm. The results are shown in Table 1.
< example 4 >
A polyimide varnish was prepared in the same manner as in example 1 except that 30.629g (0.08790 mol) of 9, 9-bis (4-aminophenyl) fluorene (manufactured by Taoka Chemical co., ltd.) was changed from 34.845g (0.100 mol), and 16.214g (0.01210 mol) of amino-modified silicone oil "X-22-9409" (manufactured by shin-Etsu Chemical Co., Ltd.) at both ends was added, to obtain a polyimide varnish having a solid content of 20 mass%. Using the obtained polyimide varnish, a film was produced in the same manner as in example 1 to obtain a film having a thickness of 10 μm. The results are shown in Table 1.
< example 5 >
A polyimide varnish was prepared in the same manner as in example 1 except that the amount of 9, 9-bis (4-aminophenyl) fluorene (manufactured by Taoka Chemical co., ltd.) was changed from 34.845g (0.100 mol) to 15.450g (0.04434 mol), and 11.010g (0.04434 mol) of bis (4-aminophenyl) sulfone (manufactured by singapon seiko industries co., ltd.) and 15.169g (0.01132 mol) of double-terminal amino-modified silicone oil "X-22-9409" (manufactured by shin-shio Chemical industries co., ltd.) were added, thereby obtaining a polyimide varnish having a solid content of 20 mass%. Using the obtained polyimide varnish, a film was produced in the same manner as in example 1 to obtain a film having a thickness of 8 μm. The results are shown in Table 1.
< example 6 >
A polyimide varnish was prepared in the same manner as in example 5 except that the amount of 9, 9-bis (4-aminophenyl) fluorene (manufactured by Taoka Chemical co., ltd.) was changed from 15.450g (0.04434 mol) to 15.360g (0.04408 mol), the amount of bis (4-aminophenyl) sulfone (manufactured by singham refining industries co., ltd.) was changed from 11.010g (0.04434 mol) to 14.116g (0.04408 mol) of 2, 2' -bis (trifluoromethyl) benzidine (manufactured by singham refining industries ltd.), and the amount of amino-modified silicone oil "X-22-9409" (manufactured by shin-shi Chemical industries ltd.) was changed from 15.169g (0.01132 mol) to 15.879g (0.01184 mol), thereby obtaining a polyimide varnish having a solid content of 20 mass%. Using the obtained polyimide varnish, a film was produced in the same manner as in example 1 to obtain a film having a thickness of 9 μm. The results are shown in Table 1.
< example 7 >
A polyimide varnish was prepared in the same manner as in example 6 except that the amount of 9, 9-bis (4-aminophenyl) fluorene (manufactured by Taoka Chemical co., ltd.) was changed from 15.360g (0.04408 mol) to 16.471g (0.04727 mol), the amount of 2, 2' -bis (trifluoromethyl) benzidine (manufactured by singapon seiki industries co) was changed from 14.116g (0.04408 mol) to 15.138g (0.04727 mol), and the amount of amino-modified silicone oil "X-22-9409" (manufactured by shin-Etsu Chemical Co., Ltd.) at both terminals was changed from 15.879g (0.01184 mol) to 7.316g (0.00546 mol), thereby obtaining a polyimide varnish having a solid content of 20 mass%. Using the obtained polyimide varnish, a film was produced in the same manner as in example 1 to obtain a film having a thickness of 8 μm. The results are shown in Table 1.
< comparative example 1 >
A polyimide varnish was prepared in the same manner as in example 1 except that the amount of 1,2,4, 5-cyclohexanetetracarboxylic dianhydride (manufactured by Mitsubishi gas Chemical Co., Ltd.) was changed from 11.209g (0.050 mol) to 22.417g (0.100 mol), and 22.922g (0.050 mol) of 9, 9' -bis (3, 4-dicarboxyphenyl) fluorene dianhydride (manufactured by JFE Chemical Corporation) was not added, whereby a polyimide varnish having a solid content of 20 mass% was obtained. Using the obtained polyimide varnish, a film was produced in the same manner as in example 1 to obtain a film having a thickness of 11 μm. The results are shown in Table 2.
< comparative example 2 >
A polyimide varnish was prepared in the same manner as in comparative example 1 except that 34.845g (0.100 mol) of 9, 9-bis (4-aminophenyl) fluorene (manufactured by Taoka Chemical co., ltd.) was changed to 32.024g (0.100 mol) of 2, 2' -bis (trifluoromethyl) benzidine (manufactured by singham & mountain refinement industries, ltd.) to obtain a polyimide varnish having a solid content of 20 mass%. Using the obtained polyimide varnish, a film was produced in the same manner as in example 1 to obtain a film having a thickness of 9 μm. The results are shown in Table 2.
< comparative example 3 >
A polyimide varnish was prepared in the same manner as in example 4 except that 22.922g (0.050 mol) of 9,9 ' -bis (3, 4-dicarboxyphenyl) fluorene dianhydride (manufactured by JFE Chemical Corporation) was changed to 14.710g (0.050 mol) of 3,3 ', 4,4 ' -biphenyltetracarboxylic dianhydride (s-BPDA) (manufactured by mitsubishi Chemical Corporation), the amount of 9, 9-bis (4-aminophenyl) fluorene (manufactured by Taoka Chemical co., ltd.) was changed from 30.629g (0.08790 mol) to 31.064g (0.08915 mol), and the amount of amino group-modified silicone oil "X-22-9409" (manufactured by shin-over Chemical industries) was changed from 16.214g (0.01210 mol) to 14.539g (0.01085 mol), thereby obtaining a polyimide varnish having a solid content of 20 mass%. Using the obtained polyimide varnish, a film was produced in the same manner as in example 1 to obtain a film having a thickness of 15 μm. The results are shown in Table 2.
< comparative example 4 >
A polyimide varnish was prepared in the same manner as in example 1 except that 22.922g (0.050 mol) of 9,9 ' -bis (3, 4-dicarboxyphenyl) fluorene dianhydride (manufactured by JFE Chemical Corporation) was changed to 14.710g (0.050 mol) of 3,3 ', 4,4 ' -biphenyltetracarboxylic dianhydride (s-BPDA) (manufactured by Mitsubishi Chemical Corporation), and a polyimide varnish having a solid content of 20 mass% was obtained. Using the obtained polyimide varnish, a film was produced in the same manner as in example 1 to obtain a film having a thickness of 8 μm. The results are shown in Table 2.
[ Table 1]
Figure BDA0002434705300000201
[ Table 2]
TABLE 2
Figure BDA0002434705300000211
Abbreviations in tables 1 and 2 are as follows.
HPMDA: 1,2,4, 5-Cyclohexanetetracarboxylic dianhydride (Compound represented by the formula (a-1))
BPAF: 9, 9' -bis (3, 4-dicarboxyphenyl) fluorene dianhydride (compound represented by formula (a-2))
BPDA: 3,3 ', 4, 4' -biphenyltetracarboxylic dianhydride
BAFL: 9, 9-bis (4-aminophenyl) fluorene (compound represented by the formula (b-1))
4, 4-DDS: bis (4-aminophenyl) sulfone (compound represented by the formula (b-2-1))
TFMB: 2, 2' -bis (trifluoromethyl) benzidine (compound represented by the formula (b-2-2))
X-22-9409: amino-modified Silicone oil at both ends (Compound represented by formula (b-2-3))
As shown in Table 1, the polyimide films of examples 1 to 7 were excellent in colorless transparency, optical isotropy and laser peelability. In addition, the polyimide films of examples 3 to 7 also have low water absorption.
On the other hand, as shown in table 2, the polyimide film of comparative example 1 was very poor in laser peelability, the polyimide film of comparative example 2 was very poor in optical isotropy and laser peelability, and the polyimide films of comparative examples 3 and 4 were very poor in colorless transparency.

Claims (7)

1. A polyimide resin comprising: a structural unit A derived from a tetracarboxylic dianhydride and a structural unit B derived from a diamine,
the structural unit A comprises a structural unit (A-1) derived from a compound represented by the following formula (a-1) and a structural unit (A-2) derived from a compound represented by the following formula (a-2),
the structural unit B comprises a structural unit (B-1) derived from a compound represented by the following formula (B-1), the proportion of the structural unit (B-1) in the structural unit B is 30 to 100 mol%,
Figure FDA0003673267260000011
in the formula (b-1), R is each independently a hydrogen atom, a fluorine atom or a methyl group.
2. The polyimide resin according to claim 1, wherein the proportion of the structural unit (A-1) in the structural unit A is 10 to 90 mol%,
the proportion of the structural unit (A-2) in the structural unit A is 10 to 90 mol%.
3. The polyimide resin according to claim 1 or 2, wherein the structural unit B further comprises a structural unit (B-2), and the structural unit (B-2) is at least 1 selected from the group consisting of a structural unit (B-2-1) derived from a compound represented by the following formula (B-2-1), a structural unit (B-2-2) derived from a compound represented by the following formula (B-2-2), and a structural unit (B-2-3) derived from a compound represented by the following formula (B-2-3),
Figure FDA0003673267260000021
in the formula (b-2-3),
R 1 ～R 4 each independently a monovalent aliphatic radical or a monovalent aromatic radical,
Z 1 and Z 2 Each independently a divalent aliphatic group or a divalent aromatic group,
r is a positive integer.
4. The polyimide resin according to claim 3, wherein the proportion of the structural unit (B-1) in the structural unit B is 30 to 95 mol%,
the proportion of the structural unit (B-2) in the structural unit B is 5 to 70 mol%.
5. The polyimide resin according to claim 1 or 2, wherein R represents a hydrogen atom.
6. A polyimide varnish obtained by dissolving the polyimide resin according to any one of claims 1 to 5 in an organic solvent.
7. A polyimide film comprising the polyimide resin according to any one of claims 1 to 5.
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