KR20210096064A - Polyimide resins, polyimide varnishes and polyimide films - Google Patents

Abstract

(식(b-2-2) 중, R은 각각 독립적으로, 수소원자, 불소원자 또는 메틸기이며, 식(b-2-4) 중, R¹~R⁴는, 각각 독립적으로, 1가의 지방족기 또는 1가의 방향족기이며, Z¹ 및 Z²는, 각각 독립적으로, 2가의 지방족기 또는 2가의 방향족기이며, r은, 양의 정수이다.)A polyimide resin having a structural unit A derived from tetracarboxylic dianhydride and a structural unit B derived from diamine, wherein the structural unit A is a structural unit derived from a compound represented by the following formula (a-1-1) (A) -1-1) and at least one structural unit (A-1) selected from the group consisting of a structural unit (A-1-2) derived from a compound represented by the following formula (a-1-2); , structural unit B is a structural unit derived from a compound represented by the following formula (b-1) (B-1), and a structural unit derived from a compound represented by the following formula (b-2-1) (B-2) -1), a structural unit derived from a compound represented by the following formula (b-2-2) (B-2-2), a structural unit derived from a compound represented by the following formula (b-2-3) (B) -2-3), a structural unit derived from a compound represented by the following formula (b-2-4) (B-2-4), and a structural unit derived from a compound represented by the following formula (b-2-5) A polyi containing at least one structural unit (B-2) selected from the group consisting of units (B-2-5), wherein the proportion of the structural unit (B-1) in the structural unit B is 70 mol% or more. A mid resin, and a polyimide varnish and polyimide film comprising the polyimide resin.

(In formula (b-2-2), each R is independently a hydrogen atom, a fluorine atom, or a methyl group, and in the formula (b-2-4), R ¹ to R ⁴ are each independently a monovalent aliphatic a group or a monovalent aromatic group, Z ¹ and Z ² are each independently a divalent aliphatic group or a divalent aromatic group, and r is a positive integer.)

Description

Polyimide resins, polyimide varnishes and polyimide films

The present invention relates to polyimide resins, polyimide varnishes and polyimide films.

Various uses of polyimide resin are considered in the field|area, such as an electric/electronic component. For example, it is desired to replace a glass substrate used in an image display apparatus such as a liquid crystal display or an OLED display with a plastic substrate for the purpose of weight reduction or flexibility of the device, and a polyimide film suitable as the plastic substrate research is in progress.

In an image display device, when light emitted from a display element is emitted through a plastic substrate, colorless transparency is required for the plastic substrate, and further, when light passes through a retardation film or a polarizing plate (for example, a liquid crystal display, A touch panel or the like) is required to have high optical isotropy (that is, low Rth) in addition to colorless transparency.

In order to satisfy the performance requirements as described above, various polyimide resins are being developed. For example, in Patent Document 1, 3,3'-diaminodiphenylsulfone (1st diamine) and 4,4' are polyimide resins that provide a colorless, transparent, low Rth and excellent toughness polyimide film. - A polyimide resin prepared by using a combination of a specific diamine (second diamine) such as diaminodiphenylsulfone as a diamine component is described.

International Publication No. 2016/158825

However, in order for a polyimide film to be suitable as a substrate, not only colorless transparency and optical isotropy but also chemical resistance (solvent resistance, acid resistance and alkali resistance) are important physical properties.

For example, when a varnish for forming the resin layer is applied to the polyimide film to form another resin layer (eg, color filter, resist) on the polyimide film, the polyimide film contains the varnish Resistance to the contained solvent is required. When the solvent resistance of a polyimide film is insufficient, there exists a possibility that a meaning as a board|substrate may not be achieved by melt|dissolution or swelling of a film.

Moreover, when a polyimide film is used as a board|substrate for ITO (Indium Tin Oxide) film|membrane formation, resistance with respect to the acid used for the etching of an ITO film is calculated|required of the polyimide film. If the acid resistance of the polyimide film is insufficient, the film may yellow and the colorless transparency may be impaired.

In addition, alkaline aqueous solutions, such as sodium hydroxide aqueous solution and potassium hydroxide aqueous solution, are mainly used for washing|cleaning of supports, such as a glass plate, used when manufacturing a polyimide film (a support body to which a polyimide varnish is apply|coated). Washing with an aqueous alkaline solution may be performed even in the state in which the polyimide film was formed into a film on support bodies, such as a glass plate. Therefore, resistance to alkali is also required for the polyimide film.

However, in Patent Document 1, chemical resistance is not evaluated.

The present invention has been made in view of this situation, and the object of the present invention is a polyimide resin capable of forming a film excellent in colorless transparency, optical isotropy, and chemical resistance (solvent resistance, acid resistance and alkali resistance), and this polyimide To provide a polyimide varnish and a polyimide film containing a resin.

MEANS TO SOLVE THE PROBLEM The present inventors discovered that the said subject could be solved by the polyimide resin containing the combination of specific structural unit, and came to complete invention.

That is, the present invention relates to the following [1] to [10].

[One]

A polyimide resin having a structural unit A derived from tetracarboxylic dianhydride and a structural unit B derived from diamine,

The structural unit A is a structural unit (A-1-1) derived from a compound represented by the following formula (a-1-1) and a structural unit (A) derived from a compound represented by the following formula (a-1-2) It contains at least one structural unit (A-1) selected from the group consisting of -1,2),

The structural unit B is a structural unit derived from a compound represented by the following formula (b-1) (B-1), and a structural unit derived from a compound represented by the following formula (b-2-1) (B-2-) 1), a structural unit derived from a compound represented by the following formula (b-2-2) (B-2-2), a structural unit derived from a compound represented by the following formula (b-2-3) (B- 2-3), a structural unit derived from a compound represented by the following formula (b-2-4) (B-2-4), and a structural unit derived from a compound represented by the following formula (b-2-5) (B-2-5) comprising at least one structural unit (B-2) selected from the group consisting of,

The polyimide resin whose ratio of the structural unit (B-1) in structural unit B is 70 mol% or more.

[Formula 1]

(in formula (b-2-2),

R is each independently a hydrogen atom, a fluorine atom or a methyl group,

In formula (b-2-4),

R ¹ to R ⁴ are each independently a monovalent aliphatic group or a monovalent aromatic group,

Z ¹ and Z ² are each independently a divalent aliphatic group or a divalent aromatic group,

r is a positive integer.)

[2]

The proportion of the structural unit (B-1) in the structural unit B is 70 to 97 mol%,

The polyimide resin according to the above [1], wherein the proportion of the structural unit (B-2) in the structural unit B is 3 to 30 mol%.

[3]

The polyimide resin according to the above [1] or [2], wherein the proportion of the structural unit (A-1) in the structural unit A is 50 mol% or more.

[4]

The polyimide resin according to any one of [1] to [3], wherein the structural unit (B-2) is a structural unit (B-2-1).

[5]

The polyimide resin according to any one of [1] to [3], wherein the structural unit (B-2) is a structural unit (B-2-2).

[6]

The polyimide resin according to any one of [1] to [3], wherein the structural unit (B-2) is a structural unit (B-2-3).

[7]

The polyimide resin according to any one of [1] to [3], wherein the structural unit (B-2) is a structural unit (B-2-4).

[8]

The polyimide resin according to any one of [1] to [3], wherein the structural unit (B-2) is a structural unit (B-2-5).

[9]

A polyimide varnish obtained by dissolving the polyimide resin according to any one of [1] to [8] in an organic solvent.

[10]

A polyimide film comprising the polyimide resin according to any one of [1] to [8].

According to the present invention, a film having excellent colorless transparency, optical isotropy, and chemical resistance (solvent resistance, acid resistance and alkali resistance) can be formed.

[Polyimide resin]

The polyimide resin of the present invention has a structural unit A derived from tetracarboxylic dianhydride and a structural unit B derived from diamine, wherein the structural unit A is derived from a compound represented by the following formula (a-1-1) A structural unit (A-1) which is at least one selected from the group consisting of a structural unit (A-1-1) and a structural unit (A-1-2) derived from a compound represented by the following formula (a-1-2) (A-1) ), and the structural unit B is a structural unit derived from a compound represented by the following formula (b-1) (B-1), and a structural unit derived from a compound represented by the following formula (b-2-1) (B-2-1), a structural unit derived from a compound represented by the following formula (b-2-2) (B-2-2), derived from a compound represented by the following formula (b-2-3) A structural unit (B-2-3), a structural unit derived from a compound represented by the following formula (b-2-4) (B-2-4), and a compound represented by the following formula (b-2-5) contains at least one structural unit (B-2) selected from the group consisting of structural units (B-2-5) derived from % or more

[Formula 2]

(in formula (b-2-2),

R is each independently a hydrogen atom, a fluorine atom or a methyl group,

In formula (b-2-4),

R ¹ to R ⁴ are each independently a monovalent aliphatic group or a monovalent aromatic group,

Z ¹ and Z ² are each independently a divalent aliphatic group or a divalent aromatic group,

r is a positive integer.)

<composition unit A>

The structural unit A is a structural unit derived from tetracarboxylic dianhydride in the polyimide resin, and a structural unit derived from a compound represented by the following formula (a-1-1) (A-1-1) and the following formula It contains the structural unit (A-1) which is at least 1 selected from the group which consists of structural units (A-1-2) derived from the compound represented by (a-1-2).

[Formula 3]

The compound represented by formula (a-1-1) is 1,2,4,5-cyclohexanetetracarboxylic dianhydride.

When the structural unit A includes the structural unit (A-1-1) as the structural unit (A-1), colorless transparency and optical isotropy of the film can be improved.

The compound represented by formula (a-1-2) is 4,4'-oxydiphthalic anhydride.

When the structural unit A includes the structural unit (A-1-2) as the structural unit (A-1), the chemical resistance of the film can be improved.

The proportion of the structural unit (A-1) in the structural unit A is preferably 50 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 of the structural unit (A-1) is not particularly limited, that is, it is 100 mol%. The constituent unit A may consist of only the constituent unit (A-1).

The structural unit (A-1) may be only the structural unit (A-1-1) or only the structural unit (A-1-2). Further, the structural unit (A-1) may be a combination of the structural unit (A-1-1) and the structural unit (A-1-2).

When the structural unit (A-1) is a combination of the structural unit (A-1-1) and the structural unit (A-1-2), the structural unit (A-1-1)/the structural unit (A-1-2) ) is a molar ratio, preferably 5/95 to 95/5, more preferably 20/80 to 90/10 from the viewpoint of colorless transparency, optical isotropy, and chemical resistance, and 50/50 to 90/10 This is more preferable. Moreover, from a viewpoint of the toughness of the film obtained especially, 20/80-70/30 are still more preferable, and from a viewpoint of improving the optical isotropy of the film obtained especially, 60/40-95/5 are still more preferable, 70 /30-95/5 are still more preferable, and 85/15-95/5 are still more preferable.

The structural unit A may include structural units other than the structural unit (A-1). The tetracarboxylic dianhydride giving such a structural unit is not particularly limited, but pyromellitic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 9,9'-bis( Aromatic tetracarboxylic dianhydrides such as 3,4-dicarboxyphenyl)fluorene dianhydride and 4,4'-(hexafluoroisopropylidene)diphthalic anhydride (however, in formula (a-1-2) Except for the indicated compounds); 1,2,3,4-Cyclobutanetetracarboxylic dianhydride and norbornane-2-spiro-α-cyclopentanone-α′-spiro-2′′-novonane-5,5′′,6,6 alicyclic tetracarboxylic dianhydride such as ''-tetracarboxylic dianhydride (however, the compound represented by the formula (a-1-1) is excluded); and aliphatic tetracarboxylic dianhydrides such as 1,2,3,4-butanetetracarboxylic dianhydride.

On the other hand, in this specification, aromatic tetracarboxylic dianhydride means tetracarboxylic dianhydride containing one or more aromatic rings, and alicyclic tetracarboxylic dianhydride includes one or more alicyclics, and also aromatic rings means tetracarboxylic dianhydride not containing

The number of structural units arbitrarily included in the structural unit A (that is, structural units other than structural unit (A-1)) may be one, or two or more types may be sufficient as them.

<Composition B>

Structural unit B is a structural unit derived from the diamine occupied in polyimide resin, The structural unit (B-1) derived from the compound represented by following formula (b-1), and following formula (b-2-1) A structural unit derived from a compound represented by (B-2-1), a structural unit derived from a compound represented by the following formula (b-2-2) (B-2-2), a structural unit derived from a compound represented by the following formula (b-2- A structural unit derived from the compound represented by 3) (B-2-3), a structural unit derived from a compound represented by the following formula (b-2-4) (B-2-4), and the following formula (b) It contains the structural unit (B-2) which is at least 1 selected from the group which consists of structural units (B-2-5) derived from the compound represented by -2-5).

[Formula 4]

(in formula (b-2-2),

R is each independently a hydrogen atom, a fluorine atom or a methyl group,

In formula (b-2-4),

R ¹ to R ⁴ are each independently a monovalent aliphatic group or a monovalent aromatic group,

Z ¹ and Z ² are each independently a divalent aliphatic group or a divalent aromatic group,

r is a positive integer.)

The compound represented by the formula (b-1) is 3,3'-diaminodiphenylsulfone.

The compound represented by formula (b-2-1) is 4,4'-diamino-2,2'-bistrifluoromethyldiphenyl ether. In particular, from the viewpoint of toughness and acid resistance of the film, the structural unit (B-2) preferably includes a structural unit (B-2-1) derived from the compound represented by the formula (b-2-1), The structural unit B preferably includes a structural unit (B-2-1) derived from the compound represented by the formula (b-2-1).

In the formula (b-2-2), each R is independently a hydrogen atom, a fluorine atom, or a methyl group, preferably a hydrogen atom. Examples of the compound represented by the formula (b-2-2) include 9,9-bis(4-aminophenyl)fluorene, 9,9-bis(3-fluoro-4-aminophenyl)fluorene, and 9 and 9-bis(3-methyl-4-aminophenyl)fluorene, and 9,9-bis(4-aminophenyl)fluorene is preferred. In particular, from the viewpoint of heat resistance and optical isotropy of the film, the structural unit (B-2) preferably includes a structural unit (B-2-2) derived from the compound represented by the formula (b-2-2), , structural unit B preferably includes a structural unit (B-2-2) derived from the compound represented by formula (b-2-2).

The compound represented by the formula (b-2-3) is 2,2-bis(4-(4-aminophenoxy)phenyl)hexafluoropropane. In particular, from the viewpoint of colorless transparency of the film, the structural unit (B-2) preferably includes a structural unit (B-2-3) derived from the compound represented by the formula (b-2-3), The unit B preferably includes a structural unit (B-2-3) derived from the compound represented by the formula (b-2-3).

^{R 1} , R ² , R ³ and R ⁴ in the formula (b-2-4) each independently represent a monovalent aliphatic group or a monovalent aromatic group, and these may be substituted with a fluorine atom. Examples of the monovalent aliphatic group include a monovalent saturated hydrocarbon group or a monovalent unsaturated hydrocarbon group. As a monovalent saturated hydrocarbon group, a C1-C22 alkyl group is mentioned, For example, a methyl group, an ethyl group, and a propyl group can be illustrated. As a monovalent unsaturated hydrocarbon group, a C2-C22 alkenyl group is mentioned, For example, a vinyl group and a propenyl group can be illustrated. As a monovalent aromatic group, a C6-C24 aryl group, an aralkyl group, etc. can be illustrated. As R ¹ , R ² , R ³ and R ⁴ , a methyl group or a phenyl group is particularly preferable.

In addition, Z ¹ and Z ² each independently represent a divalent aliphatic group or a divalent aromatic group, and these groups may be substituted with a fluorine atom or contain an oxygen atom. When an oxygen atom is included as an ether bond, the carbon number shown below means all carbon number contained in an aliphatic group or an aromatic group. Examples of the divalent aliphatic group include a divalent saturated hydrocarbon group or a divalent unsaturated hydrocarbon group. Examples of the divalent saturated hydrocarbon group include an alkylene group having 1 to 22 carbon atoms and an alkyleneoxy group, and examples of the alkylene group include a methylene group, an ethylene group and a propylene group. Examples of the divalent unsaturated hydrocarbon group include an unsaturated hydrocarbon group having 2 to 22 carbon atoms, for example, a vinylene group, a propenylene group, an alkylene group having an unsaturated double bond at the terminal, and an alkyleneoxy group can illustrate, for example, a propyleneoxy group, a trimethyleneoxy group, or the like. Examples of the divalent aromatic group include a phenylene group having 6 to 24 carbon atoms, a phenylene group substituted with an alkyl group, an aralkylene group, and the like. As Z ¹ and Z ² , in particular, a propylene group, a phenylene group, and an aralkylene group are preferable.

Moreover, r represents a positive integer, and it is preferable that it is an integer of 10-10,000.

Examples of the compound represented by the formula (b-2-4) include 1,3-bis(3-aminopropyl)-1,1,2,2-tetramethyldisiloxane and 1,3-bis(3-aminobutyl). )-1,1,2,2-tetramethyldisiloxane, bis(4-aminophenoxy)dimethylsilane, 1,3-bis(4-aminophenoxy)tetramethyldisiloxane, 1,1,3,3 -tetramethyl-1,3-bis(4-aminophenyl)disiloxane, 1,1,3,3-tetraphenoxy-1,3-bis(2-aminoethyl)disiloxane, 1,1,3, 3-tetraphenyl-1,3-bis(2-aminoethyl)disiloxane, 1,1,3,3-tetraphenyl-1,3-bis(3-aminopropyl)disiloxane, 1,1,3, 3-tetramethyl-1,3-bis(2-aminoethyl)disiloxane, 1,1,3,3-tetramethyl-1,3-bis(3-aminopropyl)disiloxane, 1,1,3, 3-tetramethyl-1,3-bis(4-aminobutyl)disiloxane, 1,3-dimethyl-1,3-dimethoxy-1,3-bis(4-aminobutyl)disiloxane, 1,1, 3,3,5,5-hexamethyl-1,5-bis(4-aminophenyl)trisiloxane, 1,1,5,5-tetraphenyl-3,3-dimethyl-1,5-bis(3- Aminopropyl) trisiloxane, 1,1,5,5-tetraphenyl-3,3-dimethoxy-1,5-bis(4-aminobutyl)trisiloxane, 1,1,5,5-tetraphenyl-3 ,3-dimethoxy-1,5-bis(5-aminopentyl)trisiloxane, 1,1,5,5-tetramethyl-3,3-dimethoxy-1,5-bis(2-aminoethyl)tri Siloxane, 1,1,5,5-tetramethyl-3,3-dimethoxy-1,5-bis(4-aminobutyl)trisiloxane, 1,1,5,5-tetramethyl-3,3-dimethyl Toxy-1,5-bis(5-aminopentyl)trisiloxane, 1,1,3,3,5,5-hexamethyl-1,5-bis(3-aminopropyl)trisiloxane, 1,1,3 ,3,5,5-hexaethyl-1,5-bis(3-aminopropyl)trisiloxane, 1,1,3,3,5,5-hexapropyl-1,5-bis(3-aminopropyl) Trisiloxane etc. are mentioned. Said compound may be used independently, or may be used in combination of 2 or more types.

As commercially available products of the compound represented by the formula (b-2-4), "X-22-9409", "X-22-1660B", "X-22-" manufactured by Shin-Etsu Chemical Co., Ltd. 161A", "X-22-161B", etc. are mentioned.

In particular, from the viewpoint of acid resistance and transparency of the film, the structural unit (B-2) preferably includes a structural unit (B-2-4) derived from the compound represented by the formula (b-2-4), The structural unit B preferably includes a structural unit (B-2-4) derived from the compound represented by the formula (b-2-4).

The compound represented by the formula (b-2-5) is 2,2'-bis(trifluoromethyl)benzidine. In particular, from the viewpoint of toughness, heat resistance, and optical isotropy of the film, the structural unit (B-2) includes a structural unit (B-2-5) derived from the compound represented by the formula (b-2-5). Preferably, the structural unit B includes a structural unit (B-2-5) derived from the compound represented by the formula (b-2-5).

From the viewpoint of improving various performances of the film as described above, the structural unit B is a structural unit (B-2), a structural unit derived from the compound represented by the formula (b-2-1) (B-2-1) ), a structural unit derived from a compound represented by formula (b-2-2) (B-2-2), a structural unit derived from a compound represented by formula (b-2-3) (B-2-3) ), a structural unit derived from a compound represented by formula (b-2-4) (B-2-4), and a structural unit derived from a compound represented by the following formula (b-2-5) (B-2) It is preferable to include at least one selected from the group consisting of -5), and in particular, from the viewpoint of improving the colorless transparency and optical isotropy of the film, the structural unit B is a compound represented by the formula (b-2-3) It is preferable to include the derived structural unit (B-2-3).

Structural unit B contains both a structural unit (B-1) and a structural unit (B-2), and further sets the ratio of the structural unit (B-1) in the structural unit B to 70 mol% or more. , the colorless transparency, optical isotropy, and chemical resistance of the film can be improved. Among them, acid resistance and solvent resistance can be particularly improved.

The ratio of the structural unit (B-1) in the structural unit B is 70 mol% or more. From the viewpoint of acid resistance and solvent resistance, the proportion is preferably 70 to 97 mol%, more preferably 75 to 97 mol%, still more preferably 80 to 97 mol%, and from the viewpoint of acid resistance, more More preferably, it is 90-97 mol%, More preferably, it is 93-97 mol%.

The proportion of the structural unit (B-2) in the structural unit B is preferably 3 to 30 mol%, more preferably 3 to 25 mol%, and still more preferably 3 to 20 mol%. In particular, the structural unit (B-2) is at least selected from the group consisting of the structural units (B-2-1), (B-2-2), (B-2-3) and (B-2-5). In the case of one, the proportion of the structural unit (B-2) is still more preferably 10 to 25 mol%, still more preferably 10 to 20 mol%. In particular, when the structural unit (B-2) is a structural unit (B-2-4), the proportion of the structural unit (B-2) is still more preferably 3 to 15 mol%, still more preferably Preferably it is 3-10 mol%, More preferably, it is 3-7 mol%.

The proportion of the total of the structural units (B-1) and (B-2) in the structural unit B is preferably 75 mol% or more, more preferably 80 mol% or more, and still more preferably 90 mol% or more. % or more, particularly preferably 99 mol% or more. The upper limit of the ratio of the sum total of structural units (B-1) and (B-2) is not specifically limited, That is, it is 100 mol%. The structural unit B may consist of only the structural unit (B-1) and the structural unit (B-2).

The structural unit (B-2) may be only a structural unit (B-2-1), may be only a structural unit (B-2-2), may be only a structural unit (B-2-3), or may be a structural unit It may be only (B-2-4), or it may be only the structural unit (B-2-5).

In addition, the structural unit (B-2) may be a combination of two or more structural units selected from the group consisting of structural units (B-2-1) to (B-2-5).

The structural unit B may include structural units other than the structural units (B-1) and (B-2). Although it does not specifically limit as diamine giving such a structural unit, 1, 4- phenylenediamine, p-xylylene diamine, 3, 5- diamino benzoic acid, 1, 5- diamino naphthalene, 2,2'- Dimethylbiphenyl-4,4'-diamine, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 2,2-bis(4-aminophenyl)hexafluoropropane, 4 ,4'-diaminodiphenylsulfone, 4,4'-diaminobenzanilide, 1-(4-aminophenyl)-2,3-dihydro-1,3,3-trimethyl-1H-indene-5- Amine, α,α′-bis(4-aminophenyl)-1,4-diisopropylbenzene, N,N′-bis(4-aminophenyl)terephthalamide, 4,4′-bis(4-aminophenoxy) Cy) biphenyl and aromatic diamines such as 2,2-bis[4-(4-aminophenoxy)phenyl]propane (provided that the compound represented by the formula (b-1) and the formula (b-2-1) -Excluding compounds represented by formula (b-2-5)); alicyclic diamines such as 1,3-bis(aminomethyl)cyclohexane and 1,4-bis(aminomethyl)cyclohexane; and aliphatic diamines such as ethylenediamine and hexamethylenediamine (however, the compound represented by the formula (b-2-4) is excluded).

On the other hand, in the present specification, 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 the aliphatic diamine is It means diamine which contains neither an aromatic ring nor an alicyclic ring.

The number of structural units arbitrarily included in structural unit B (that is, structural units other than structural units (B-1) and (B-2)) may be one, or two or more types may be sufficient as them.

The number average molecular weight of the polyimide resin of this invention becomes like this. From a viewpoint of the mechanical strength of the polyimide film obtained, Preferably it is 5,000-200,000. In addition, the number average molecular weight of a polyimide resin can be calculated|required from the standard polymethylmethacrylate (PMMA) conversion value by gel filtration chromatography measurement, for example.

The polyimide resin of the present invention may contain a structure other than the polyimide chain (a structure in which the structural unit A and the structural unit B are imide-bonded). As structures other than the polyimide chain which can be contained in polyimide resin, the structure etc. containing an amide bond are mentioned, for example.

The polyimide resin of the present invention preferably contains a polyimide chain (a structure in which the structural unit A and the structural unit B are imide-bonded) as a main structure. Therefore, the proportion of the polyimide chain in the polyimide resin of the present invention is preferably 50 mass % or more, more preferably 70 mass % or more, still more preferably 90 mass % or more, particularly preferably It is 99 mass % or more.

By using the polyimide resin of the present invention, a film excellent in colorless transparency, optical isotropy, and chemical resistance can be formed, and suitable physical property values of the film are as follows.

When a total light transmittance is set as a film with a thickness of 10 micrometers, Preferably it is 88 % or more, More preferably, it is 88.5 % or more, More preferably, it is 89 % or more.

The yellow index (YI) is preferably 4.0 or less, more preferably 2.5 or less, still more preferably 2.0 or less when a film having a thickness of 10 µm is obtained.

b ^* becomes like this. When it is set as the film with a thickness of 10 micrometers, Preferably it is 2.0 or less, More preferably, it is 1.2 or less, More preferably, it is 1.0 or less.

The absolute value of the thickness retardation Rth is preferably 70 nm or less, more preferably 60 nm or less, and still more preferably 50 nm or less when a film having a thickness of 10 µm is obtained.

Mixed acid ΔYI is preferably 1.5 or less, more preferably 1.3 or less, still more preferably 1.0 or less when a film having a thickness of 10 µm is obtained.

Mixed acid Δb ^* is preferably 0.8 or less, more preferably 0.6 or less, and still more preferably 0.5 or less when a film having a thickness of 10 µm is obtained.

On the other hand, mixed acid ΔYI and mixed acid Δb ^* mean the difference between ^{YI and b *} before and after immersion when the polyimide film is immersed in a mixture of phosphoric acid, nitric acid and acetic acid, respectively, specifically, Examples It can be measured by the method described in It means that it is excellent in acid resistance, so that ΔYI and Δb ^{* are small.} By using the polyimide resin of this invention, the film excellent in chemical-resistance can be formed, and the outstanding resistance also to an acid is shown. In particular, a mixed acid (for example, 50 to 97 mass% of phosphoric acid, 1 to 20 mass% of nitric acid, 1 to 10 mass% of acetic acid, and 1 to 20 mass% of water, preferably a mixed solution of phosphoric acid at 63- 87 mass %, nitric acid 5-15 mass %, acetic acid 3-7 mass %, and water shows excellent resistance with respect to the mixed solution) of 5-15 mass %.

The film that can be formed using the polyimide resin of the present invention has good mechanical properties and has the following suitable physical properties.

The tensile strength is preferably 60 MPa or more, more preferably 70 MPa or more, and still more preferably 80 MPa or more.

The tensile modulus of elasticity is preferably 2.0 GPa or more, more preferably 2.5 GPa or more, and still more preferably 3.0 GPa or more.

In addition, the film that can be formed using the polyimide resin of one embodiment of the present invention has good heat resistance and has the following suitable physical properties.

The glass transition temperature (Tg) is preferably 230°C or higher, more preferably 250°C or higher, and still more preferably 270°C or higher.

In addition, the above-mentioned physical property value in this invention can be specifically measured by the method as described in an Example.

[Method for producing polyimide resin]

The polyimide resin of the present invention contains 70 mol% or more of the tetracarboxylic acid component containing the compound providing the above-described structural unit (A-1), and the compound providing the above-mentioned structural unit (B-1) in an amount of 70 mol% or more. It can be prepared by reacting a diamine component containing a compound giving one structural unit (B-2).

Examples of the compound giving the structural unit (A-1) include, but are not limited to, the compound represented by the formula (a-1-1) and the compound represented by the formula (a-1-2), It may be a derivative thereof within the range giving the same structural unit. Examples of the derivative include tetracarboxylic acid corresponding to tetracarboxylic dianhydride represented by formulas (a-1-1) and (a-1-2), and alkyl esters of tetracarboxylic acid. As the compound giving the structural unit (A-1), compounds represented by formulas (a-1-1) and (a-1-2) (that is, dianhydride) are preferable.

The tetracarboxylic acid component preferably contains 50 mol% or more of the compound providing the structural unit (A-1), more preferably contains 70 mol% or more, further preferably contains 90 mol% or more, , Especially preferably, it contains 99 mol% or more. The upper limit of the content rate of the compound giving the structural unit (A-1) is not particularly limited, that is, it is 100 mol%. The tetracarboxylic acid component may consist only of a compound giving the structural unit (A-1).

The compound providing the structural unit (A-1) may be only the compound providing the structural unit (A-1-1), or may be only the compound providing the structural unit (A-1-2). Further, the compound providing the structural unit (A-1) may be a combination of the compound providing the structural unit (A-1-1) and the compound providing the structural unit (A-1-2).

When the compound giving the structural unit (A-1) is a combination of the compound giving the structural unit (A-1-1) and the compound giving the structural unit (A-1-2), the structural unit (A-1) The content ratio of the compound giving -1) / compound giving the structural unit (A-1-2) is preferably 5/95 to 95/5 in molar ratio, and from the viewpoint of colorless transparency, optical isotropy and chemical resistance , 20/80 to 90/10 are more preferable, and 50/50 to 90/10 are still more preferable. Moreover, from a viewpoint of the toughness of the film obtained especially, 20/80-70/30 are still more preferable, and from a viewpoint of improving the optical isotropy of the film obtained especially, 60/40-95/5 are still more preferable, 70 /30-95/5 are still more preferable, and 85/15-95/5 are still more preferable.

The tetracarboxylic acid component may contain compounds other than the compound giving the structural unit (A-1), and examples of the compound include the above-mentioned aromatic tetracarboxylic dianhydride, alicyclic tetracarboxylic dianhydride, and aliphatic. tetracarboxylic dianhydride, and their derivatives (tetracarboxylic acid, an alkyl ester of tetracarboxylic acid, etc.) are mentioned.

The number of compounds arbitrarily contained in the tetracarboxylic acid component (that is, compounds other than the compound which gives a structural unit (A-1)) may be one, or 2 or more types may be sufficient as them.

Although the compound represented by Formula (b-1) is mentioned as a compound which provides a structural unit (B-1), It is not limited to it, It may be a derivative|guide_body within the range which gives the same structural unit. As this derivative, the diisocyanate corresponding to the diamine represented by Formula (b-1) is mentioned. As a compound which provides a structural unit (B-1), the compound (namely, diamine) represented by Formula (b-1) is preferable.

As a compound which gives a structural unit (B-2), it is represented by a compound represented by a formula (b-2-1), a compound represented by a formula (b-2-2), and a formula (b-2-3) compound, a compound represented by the formula (b-2-4), and a compound represented by the formula (b-2-5) are mentioned, but it is not limited thereto, within the range that can form the same structural unit. It may be a derivative thereof. As this derivative, the diisocyanate corresponding to the diamine represented by a formula (b-2-1) - a formula (b-2-5) is mentioned. As a compound which provides a structural unit (B-2), the compound (ie, diamine) represented by a formula (b-2-1) - a formula (b-2-5) is preferable.

The diamine component contains 70 mol% or more of the compound which provides a structural unit (B-1). The diamine component contains preferably 70 to 97 mol%, more preferably 75 to 97 mol%, and still more preferably 80 to 97 mol% of the compound giving the structural unit (B-1). And from a viewpoint of acid resistance, More preferably, it contains 90-97 mol%, More preferably, it contains 93-97 mol%.

The diamine component contains preferably 3 to 30 mol%, more preferably 3 to 25 mol%, and still more preferably 3 to 20 mol% of the compound giving the structural unit (B-2). do. In particular, the compound providing the structural unit (B-2) is a compound giving the structural unit (B-2-1), the compound giving (B-2-2), (B-2-3) In the case of at least one member selected from the group consisting of a compound and a compound imparting (B-2-5), the diamine component is more preferably 10 to 25 moles of the compound providing the structural unit (B-2). %, and more preferably 10 to 20 mol%. Moreover, especially when the compound which provides a structural unit (B-2) is a compound which provides a structural unit (B-2-4), a diamine component is more than the compound which provides a structural unit (B-2). More preferably, it contains 3-15 mol%, More preferably, it contains 3-10 mol%, More preferably, it contains 3-7 mol%.

The diamine component contains, in total, preferably 75 mol% or more, and more preferably 80 mol% or more of the compound providing the structural unit (B-1) and the compound giving the structural unit (B-2) in total. and more preferably 90 mol% or more, and particularly preferably 99 mol% or more. The upper limit of the content ratio of the total of the compound giving the structural unit (B-1) and the compound giving the structural unit (B-2) is not particularly limited, that is, it is 100 mol%. The diamine component may consist only of a compound providing the structural unit (B-1) and a compound providing the structural unit (B-2).

The compound providing the structural unit (B-2) may be only a compound providing the structural unit (B-2-1), or may be only a compound providing the structural unit (B-2-2), or the structural unit (B-2-2) It may be only the compound which provides B-2-3), it may be only the compound which provides the structural unit (B-2-4), or it may be only the compound which provides the structural unit (B-2-5).

Further, the compound providing the structural unit (B-2) may be a combination of two or more compounds selected from the group consisting of compounds giving the structural units (B-2-1) to (B-2-5). there is.

The diamine component may include compounds other than the compound imparting the structural unit (B-1) and the compound imparting the structural unit (B-2). Examples of the compound include the aforementioned aromatic diamines, alicyclic diamines, and aliphatic diamines and their derivatives (such as diisocyanate).

The number of compounds arbitrarily included in the diamine component (that is, compounds other than the compound which provides a structural unit (B-1) and the compound which provides a structural unit (B-2)) may be 1 type, or 2 or more types may be sufficient as it.

In the present invention, it is preferable that the input ratio of the tetracarboxylic acid component and the diamine component used in the production of the polyimide resin is 0.9 to 1.1 moles of the diamine component per 1 mole of the tetracarboxylic acid component.

Further, in the present invention, for the production of the polyimide resin, in addition to the tetracarboxylic acid component and the diamine component described above, an end capping agent may be used. As the terminal blocker, monoamines or dicarboxylic acids are preferable. The amount of the terminal blocker 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. Monoamine end caps include, for example, methylamine, ethylamine, propylamine, butylamine, benzylamine, 4-methylbenzylamine, 4-ethylbenzylamine, 4-dodecylbenzylamine, 3-methylbenzylamine , 3-ethylbenzylamine, aniline, 3-methylaniline, 4-methylaniline, etc. are recommended. Among these, benzylamine and aniline can be used suitably. As the dicarboxylic acid end capping agent, dicarboxylic acids are preferable, and a part thereof may be ring-closed. For example, phthalic acid, phthalic anhydride, 4-chlorophthalic acid, tetrafluorophthalic acid, 2,3-benzophenonedicarboxylic acid, 3,4-benzophenonedicarboxylic acid, cyclopentane-1,2-dicarboxylic acid, 4-cyclohexene-1,2-dicarboxylic acid and the like are recommended. Among these, phthalic acid and phthalic anhydride can be used suitably.

There is no restriction|limiting in particular in the method of making the above-mentioned tetracarboxylic acid component and diamine component react, A well-known method can be used.

As a specific reaction method, (1) a tetracarboxylic acid component, a diamine component, and a reaction solvent are put into a reactor, stirred at room temperature (about 20° C.) to 80° C. for 0.5 to 30 hours, and then the temperature is raised for imidization reaction (2) After dissolving the diamine component and the reaction solvent in the reactor, the tetracarboxylic acid component is added and, if necessary, stirred at room temperature (about 20° C.) to 80° C. for 0.5 to 30 hours, and the and a method in which an imidation reaction is performed by subsequently raising the temperature, (3) a method in which a tetracarboxylic acid component, a diamine component, and a reaction solvent are put into a reactor, and the temperature is raised immediately to carry out the imidization reaction, and the like.

The reaction solvent used for manufacture of a polyimide resin should just be what can melt|dissolve the polyimide produced|generated without inhibiting imidation reaction. For example, an aprotic solvent, a phenol type solvent, an ether type solvent, a carbonate type solvent, etc. are mentioned.

Specific examples of the aprotic solvent include N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam, and 1,3-dimethylimidazoli. Amide solvents such as dinon and tetramethylurea, Lactone solvents such as γ-butyrolactone and γ-valerolactone, Phosphorus-containing amide solvents such as hexamethylphosphoricamide and hexamethylphosphine triamide, dimethylsulfone , sulfur-containing solvents such as dimethyl sulfoxide and sulfolane, ketone solvents such as acetone, cyclohexanone, and methylcyclohexanone, amine solvents such as picoline and pyridine, acetic acid (2-methoxy-1-methylethyl ) and the like ester solvents.

Specific examples of the phenolic solvent 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, etc. are mentioned.

Specific examples of the ether solvent include 1,2-dimethoxyethane, bis(2-methoxyethyl)ether, 1,2-bis(2-methoxyethoxy)ethane, bis[2-(2-methyl) ethoxy)ethyl]ether, tetrahydrofuran, 1,4-dioxane, and the like.

In addition, specific examples of the carbonate-based solvent include diethyl carbonate, methyl ethyl carbonate, ethylene carbonate, propylene carbonate, and the like.

Among the above reaction solvents, amide solvents or lactone solvents are preferable. In addition, the above reaction solvents may be used alone or in mixture of two or more.

In the imidation reaction, it is preferable to use a Dean-Stark apparatus or the like to perform the reaction while removing water generated during production. By performing such operation, polymerization degree and imidation rate can be raised more.

In the above imidation reaction, a known imidation catalyst can be used. Examples of the imidization catalyst include a base catalyst or an acid catalyst.

Examples of the base catalyst include pyridine, quinoline, isoquinoline, α-picoline, β-picoline, 2,4-lutidine, 2,6-lutidine, trimethylamine, triethylamine, tripropylamine, tributylamine , triethylenediamine, imidazole, N,N-dimethylaniline, N,N-diethylaniline, etc. organic base catalyst, potassium hydroxide, sodium hydroxide, potassium carbonate, sodium carbonate, potassium hydrogen carbonate, sodium hydrogen carbonate, etc. inorganic base catalysts.

Examples of the acid catalyst include crotonic acid, acrylic acid, trans-3-hexenoic acid, cinnamic acid, benzoic acid, methylbenzoic acid, oxybenzoic acid, terephthalic acid, benzenesulfonic acid, paratoluenesulfonic acid, and naphthalenesulfonic acid. The above imidation catalysts may be used alone or in combination of two or more.

Among the above, from the viewpoint of handling properties, it is preferable to use a base catalyst, more preferably to use an organic base catalyst, still more preferably to use triethylamine, and particularly preferably to use a combination of triethylamine and triethylenediamine. do.

The temperature of the imidation reaction is preferably 120 to 250°C, more preferably 160 to 200°C from the viewpoint of suppression of reaction rate and gelation. Further, the reaction time is preferably 0.5 to 10 hours after the start of the outflow of the product 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 contains the polyimide resin of the present invention and an organic solvent, and the polyimide resin is dissolved in the organic solvent.

The organic solvent may be one in which the polyimide resin is dissolved, and is not particularly limited, but as a reaction solvent used in the production of the polyimide resin, it is preferable to use the above-mentioned compounds alone or in a mixture of two or more.

The polyimide varnish of the present invention may be a polyimide solution in which the polyimide resin obtained by the polymerization method is dissolved in a reaction solvent itself, or may be a product obtained by adding a diluent solvent to the polyimide solution.

Since the polyimide resin of this invention has solvent solubility, it can be set as the high-concentration varnish which is stable at room temperature. It is preferable that 5-40 mass % of polyimide resins of this invention are included, and, as for the polyimide varnish of this invention, it is more preferable that 10-30 mass % is included. 1-200 Pa.s is preferable and, as for the viscosity of a polyimide varnish, 2-100 Pa.s is more preferable. The viscosity of the polyimide varnish is a value measured at 25°C using an E-type viscometer.

In addition, the polyimide varnish of the present invention contains inorganic fillers, adhesion promoters, release agents, flame retardants, UV stabilizers, surfactants, leveling agents, defoamers, optical brighteners, crosslinking agents, It may contain various additives, such as a polymerization initiator and a photosensitizer.

The manufacturing method of the polyimide varnish of this invention is not specifically limited, A well-known method is applicable.

[Polyimide Film]

The polyimide film of this invention contains the polyimide resin of this invention. Accordingly, the polyimide film of the present invention is excellent in colorless transparency, optical isotropy, and chemical resistance (solvent resistance, acid resistance and alkali resistance). Suitable physical property values of the polyimide film of the present invention are as described above.

There is no restriction|limiting in particular in the manufacturing method of the polyimide film of this invention, A well-known method can be used. For example, after the polyimide varnish of the present invention is coated on a smooth support such as a glass plate, a metal plate, or a plastic, or molded into a film, an organic solvent such as a reaction solvent or a diluent solvent contained in the varnish is heated. and a method of removing it by

As a coating method, well-known coating methods, such as spin coating, slit coating, and blade coating, are mentioned. Especially, a slit coat is preferable from a viewpoint of workability|operativity that chemical-resistance is improved by controlling an intermolecular orientation.

As a method of removing the organic solvent contained in the varnish by heating, after evaporating the organic solvent at a temperature of 150° C. or less to make it tack-free, the temperature above the boiling point of the used organic solvent (not particularly limited, but preferably 200 It is preferred to dry at ~500°C). In addition, it is preferable to dry under an air atmosphere or a nitrogen atmosphere. The pressure of the dry atmosphere may be any of reduced pressure, normal pressure, and pressurization.

The method of peeling the polyimide film formed on the support from the support is not particularly limited, but includes a laser lift-off method and a method using a sacrificial layer for peeling (a method of applying a release agent to the surface of the support in advance). there is.

Moreover, the polyimide film of this invention can also be manufactured using the polyamic-acid varnish in which polyamic acid is melt|dissolved in the organic solvent.

The polyamic acid contained in the polyamic acid varnish includes, as a precursor of the polyimide resin of the present invention, a tetracarboxylic acid component containing a compound giving the above-mentioned structural unit (A-1), and the above-mentioned structural unit (B). It is a product of the polyaddition reaction of a diamine component containing 70 mol% or more of the compound giving -1) and the compound giving the above-mentioned structural unit (B-2). By imidating this polyamic acid (ring closure by dehydration), the polyimide resin of the present invention as a final product is obtained.

As the organic solvent contained in the polyamic acid varnish, the organic solvent contained in the polyimide varnish of the present invention may be used.

In the present invention, the polyamic acid varnish may be a polyamic acid solution itself obtained by polyaddition reaction of a tetracarboxylic acid component and a diamine component in a reaction solvent, or a further diluent solvent is added to the polyamic acid solution. it may have been

There is no restriction|limiting in particular in the method of manufacturing a polyimide film using a polyamic-acid varnish, A well-known method can be used. For example, a polyamic acid varnish is applied on a smooth support such as a glass plate, a metal plate, or a plastic, or molded into a film, and an organic solvent such as a reaction solvent or a diluent solvent contained in the varnish is removed by heating. Thus, a polyamic acid film is obtained, and the polyamic acid in the polyamic acid film is imidized by heating to produce a polyimide film.

The heating temperature for drying the polyamic acid varnish to obtain a polyamic acid film is preferably 50 to 120°C. As a heating temperature at the time of imidating polyamic acid by heating, Preferably it is 200-400 degreeC.

On the other hand, the imidation method is not limited to thermal imidization, and chemical imidization can also be applied.

Although the thickness of the polyimide film of this invention can be suitably selected according to a use etc., Preferably it is 1-250 micrometers, More preferably, it is 5-100 micrometers, More preferably, it is the range of 10-80 micrometers. Practical use as a self-supporting film becomes possible because thickness is 1-250 micrometers.

The thickness of the polyimide film can be easily controlled by adjusting the solid content concentration and viscosity of the polyimide varnish.

The polyimide film of this invention is used suitably as a film for various members, such as a color filter, a flexible display, a semiconductor component, and an optical member. The polyimide film of this invention is used especially suitably as a board|substrate of image display apparatuses, such as a liquid crystal display and an OLED display.

Example

Hereinafter, the present invention will be specifically described by way of Examples. However, the present invention is not limited by these Examples at all.

In Examples and Comparative Examples, each physical property was measured by the method shown below.

(1) Film thickness

The film thickness was measured using a micrometer manufactured by Mitsutoyo Co., Ltd.

(2) Tensile strength, tensile modulus of elasticity

Tensile strength and tensile modulus of elasticity were measured in accordance with JIS K7127:1999, using a tensile tester "Strograph VG-1E" manufactured by Toyo Seiki Co., Ltd. The distance between chucks was 50 mm, the specimen size was 10 mm × 70 mm, and the test speed was 20 mm/min.

(3) Glass transition temperature (Tg)

Using the thermomechanical analysis device “TMA/SS6100” manufactured by Hitachi High-Tech Sciences, Inc., the temperature sufficient to remove the residual stress under the conditions of a sample size of 2 mm×20 mm, a load of 0.1 N, and a temperature increase rate of 10° C./min in tension mode. The temperature was raised to , to remove the residual stress, and then cooled to room temperature. Thereafter, the test piece elongation was measured under the same conditions as in the treatment for removing the residual stress, and the point where the inflection point of elongation was observed was determined as the glass transition temperature.

(4) total light transmittance, yellow index (YI), b ^*

Total light transmittance, YI, and b ^* were measured in accordance with JIS K7105:1981, using a color and turbidity simultaneous measuring instrument "COH400" manufactured by Nippon Denshoku Industries Co., Ltd.

(5) Thickness phase difference (Rth)

The thickness phase difference (Rth) was measured using an ellipsometer "M-220" manufactured by Nippon Spectroscopy Co., Ltd. The value of the thickness phase difference in the measurement wavelength of 590 nm was measured. On the other hand, Rth is expressed by the following formula when the maximum in-plane refractive index of the polyimide film is nx, the minimum is ny, the refractive index in the thickness direction is nz, and the thickness of the film is d.

Rth=[{(nx+ny)/2}-nz]×d

(6) Solvent resistance

The solvent was dripped at room temperature to the polyimide film formed into a film on the glass plate, and it was confirmed whether there was no change on the film surface. In addition, as a solvent, propylene glycol monomethyl ether acetate (PGMEA) was used.

The evaluation criteria of solvent resistance were as follows.

A: There was no change in the film surface.

B: Some cracks entered the film surface.

C: A crack entered the film surface, or the film surface was dissolved.

(7) acid resistance (mixed acid ΔYI and mixed acid Δb ^* )

_{Mixed acid (H 3} PO ₄ (70 mass %) + HNO ₃ (10 mass %) + CH ₃ COOH (5 mass %) + H ₂ O (15 mass %) heated to 40 ° C. of the polyimide film formed on a glass plate of mixed solution) for 4 minutes, and then washed with water. After washing with water, the moisture was wiped off, heated on a hot plate at 240° C. for 50 minutes, and dried. ^{YI and b *} were measured before and after the test, and the changes (ΔYI and Δb ^* ) were calculated. In addition, YI measurement and b ^* measurement here were performed in the state (state of glass plate + polyimide film) which formed the polyimide film into a film on the glass plate.

(8) alkali resistance

After immersing the polyimide film formed into a film on the glass plate in the potassium hydroxide aqueous solution of 3 mass % concentration at room temperature for 5 minutes, it washed with water. After washing with water, it was checked whether there was any change in the film surface.

The evaluation criteria of alkali resistance were carried out as follows.

A: There was no change in the film surface.

B: Some cracks entered the film surface.

C: A crack entered the film surface, or the film surface was dissolved.

The tetracarboxylic acid component and diamine component used in Examples and Comparative Examples, and their abbreviations are as follows.

<Tetracarboxylic acid component>

HPMDA: 1,2,4,5-cyclohexanetetracarboxylic dianhydride (manufactured by Mitsubishi Gas Chemical Co., Ltd.; compound represented by formula (a-1-1))

ODPA: 4,4'-oxydiphthalic anhydride (manak Co., Ltd.; compound represented by formula (a-1-2))

<Diamine component>

3,3'-DDS: 3,3'-diaminodiphenylsulfone (manufactured by Seika Corporation; compound represented by formula (b-1))

6FODA: 4,4'-diamino-2,2'-bistrifluoromethyldiphenyl ether (made by ChinaTech Chemical (Tianjin) Co., Ltd.; compound represented by formula (b-2-1))

BAFL: 9,9-bis(4-aminophenyl)fluorene (manufactured by Taoka Chemical Industry Co., Ltd.; compound represented by formula (b-2-2))

HFBAPP: 2,2-bis(4-(4-aminophenoxy)phenyl)hexafluoropropane (manufactured by Seika Corporation; compound represented by formula (b-2-3))

X-22-9409: both terminal amino-modified silicone oil "X-22-9409" (manufactured by Shin-Etsu Chemical Co., Ltd.; compound represented by formula (b-2-4))

TFMB: 2,2'-bis(trifluoromethyl)benzidine (manufactured by Seika Corporation; compound represented by formula (b-2-5))

1,3-BAC: 1,3-bis(aminomethyl)cyclohexane (manufactured by Mitsubishi Gas Chemical Co., Ltd.)

4,4'-DDS: 4,4'-diaminodiphenylsulfone (manufactured by Seika Co., Ltd.)

<Example 1>

24.931 g (0.100 mol) of 3,3'-DDS was added to a 300 mL 5-neck round-bottom flask equipped with a stainless steel half-moon stirring blade, a nitrogen introduction tube, a Dean-Stark with a cooling tube, a thermometer, and a glass end cap; 6.373 g (0.005 mol) of X-22-9409 and 62.335 g of N-methylpyrrolidone (manufactured by Mitsubishi Chemical Co., Ltd.) were added, and a solution was obtained by stirring at a system temperature of 70° C., a nitrogen atmosphere, and a rotation speed of 200 rpm. .

To this solution, 32.468 g (0.105 mol) of ODPA and 15.589 g of N-methylpyrrolidone (manufactured by Mitsubishi Chemical Co., Ltd.) were added at once, followed by triethylamine (manufactured by Kanto Chemical Co., Ltd.) as an imidization catalyst. 0.529 g was added, and it was heated with a mantle heater, and the internal temperature of the reaction system was raised to 190 degreeC over about 20 minutes. The components being distilled were collected, and while the number of rotations was adjusted according to the increase in viscosity, the temperature in the reaction system was maintained at 190° C. and refluxed for 5 hours.

Thereafter, 162.057 g of N-methylpyrrolidone (manufactured by Mitsubishi Chemical Co., Ltd.) was added so that the solid content concentration was 20% by mass, and the reaction system internal temperature was cooled to 100° C. I got a mid varnish.

Subsequently, on a glass plate, the obtained polyimide varnish is applied by spin coating, held on a hot plate at 80° C. for 20 minutes, and then heated at 300° C. in a hot air dryer under nitrogen atmosphere for 30 minutes to evaporate the solvent. , a film was obtained. A result is shown in Table 1.

<Example 2>

23.121 g (0.093 mol) of 3,3'-DDS was added to a 300 mL 5-neck round-bottom flask equipped with a stainless steel semi-lunar stirring blade, a nitrogen inlet tube, a Dean-Stark with a cooling tube, a thermometer, and a glass end cap, 9.527 g (0.007 mol) of X-22-9409 and 62.182 g of N-methylpyrrolidone (manufactured by Mitsubishi Chemical Co., Ltd.) were added, and stirred at a system internal temperature of 70° C., nitrogen atmosphere, and rotation speed 200 rpm to obtain a solution. .

To this solution, 30.948 g (0.100 mol) of ODPA and 15.545 g of N-methylpyrrolidone (manufactured by Mitsubishi Chemical Co., Ltd.) were added at once, followed by triethylamine (manufactured by Kanto Chemical Co., Ltd.) as an imidization catalyst. 0.505 g was added, and it was heated with a mantle heater, and the temperature inside the reaction system was raised to 190 degreeC over about 20 minutes. The components being distilled were collected, and while the number of rotations was adjusted according to the increase in viscosity, the temperature in the reaction system was maintained at 190° C. and refluxed for 5 hours.

Thereafter, 162.273 g of N-methylpyrrolidone (manufactured by Mitsubishi Chemical Co., Ltd.) was added so that the solid content concentration was 20% by mass, and the reaction system internal temperature was cooled to 100° C. I got a mid varnish.

Subsequently, on a glass plate, the obtained polyimide varnish is applied by spin coating, held on a hot plate at 80° C. for 20 minutes, and then heated at 300° C. in a hot air dryer under nitrogen atmosphere for 30 minutes to evaporate the solvent. , a film was obtained. A result is shown in Table 1.

<Example 3>

26.174 g (0.105 mol) of 3,3'-DDS was added to a 300 mL 5-necked round-bottom flask equipped with a stainless steel semi-lunar stirring blade, a nitrogen introduction tube, a Dean-Stark with a cooling tube, a thermometer, and a glass end cap; 9.155 g (0.026 mol) of BAFL and 63.287 g of γ-butyrolactone (manufactured by Mitsubishi Chemical Co., Ltd.) were added, and stirred at a system temperature of 70° C., nitrogen atmosphere, and rotation speed 200 rpm to obtain a solution.

To this solution, 29.396 g (0.131 mol) of HPMDA and 15.822 g of γ-butyrolactone (manufactured by Mitsubishi Chemical Co., Ltd.) were added at once, followed by 0.663 triethylamine (manufactured by Kanto Chemical Co., Ltd.) as an imidization catalyst. g was added, heated with a mantle heater, and the internal temperature of the reaction system was raised to 190°C over about 20 minutes. The components being distilled were collected, and while the number of rotations was adjusted according to the increase in viscosity, the temperature in the reaction system was maintained at 190° C. and refluxed for 5 hours.

Thereafter, 160.859 g of γ-butyrolactone (manufactured by Mitsubishi Chemical Co., Ltd.) was added so that the solid content concentration was 20% by mass, the temperature inside the reaction system was cooled to 100° C. got varnish.

Subsequently, on a glass plate, the obtained polyimide varnish is applied by spin coating, held on a hot plate at 80° C. for 20 minutes, and then heated in an air atmosphere at 260° C. in a hot air dryer for 30 minutes to evaporate the solvent. , a film was obtained. A result is shown in Table 1.

<Example 4>

24.363 g (0.098 mol) of 3,3'-DDS was added to a 300 mL 5-neck round-bottom flask equipped with a stainless steel semi-lunar stirring blade, a nitrogen introduction tube, a Dean-Stark with a cooling tube, a thermometer, and a glass end cap, 12.673 g (0.024 mol) of HFBAPP and 62.967 g of γ-butyrolactone (manufactured by Mitsubishi Chemical Co., Ltd.) were added, and stirred at a system temperature of 70° C., nitrogen atmosphere, and rotation speed 200 rpm to obtain a solution.

To this solution, 27.362 g (0.122 mol) of HPMDA and 15.742 g of γ-butyrolactone (manufactured by Mitsubishi Chemical Co., Ltd.) were added at once, followed by 0.617 triethylamine (manufactured by Kanto Chemical Co., Ltd.) as an imidization catalyst. g was added, heated with a mantle heater, and the internal temperature of the reaction system was raised to 190°C over about 20 minutes. The components being distilled were collected, and while the number of rotations was adjusted according to the increase in viscosity, the temperature in the reaction system was maintained at 190° C. and refluxed for 5 hours.

Thereafter, 161.291 g of γ-butyrolactone (manufactured by Mitsubishi Chemical Co., Ltd.) was added so that the solid content concentration was 20% by mass, and the reaction system internal temperature was cooled to 100° C. got varnish.

Subsequently, on a glass plate, the obtained polyimide varnish is applied by spin coating, held on a hot plate at 80° C. for 20 minutes, and then heated in an air atmosphere at 260° C. in a hot air dryer for 30 minutes to evaporate the solvent. , a film was obtained. A result is shown in Table 1.

<Example 5>

26.319 g (0.105 mol) of 3,3'-DDS was added to a 300 mL 5-neck round-bottom flask equipped with a stainless steel semi-lunar stirring blade, a nitrogen inlet tube, a Dean-Stark with a cooling tube, a thermometer, and a glass end cap, 8.873 g (0.026 mol) of 6FODA and 63.312 g of γ-butyrolactone (manufactured by Mitsubishi Chemical Co., Ltd.) were added, and stirred at a system temperature of 70° C., nitrogen atmosphere, and rotation speed 200 rpm to obtain a solution.

To this solution, 29.559 g (0.132 mol) of HPMDA and 15.828 g of γ-butyrolactone (manufactured by Mitsubishi Chemical Co., Ltd.) were added at once, followed by 0.667 triethylamine (manufactured by Kanto Chemical Co., Ltd.) as an imidization catalyst. g was added, heated with a mantle heater, and the internal temperature of the reaction system was raised to 190°C over about 20 minutes. The components being distilled were collected, and while the number of rotations was adjusted according to the increase in viscosity, the temperature in the reaction system was maintained at 190° C. and refluxed for 5 hours.

Thereafter, 160.860 g of γ-butyrolactone (manufactured by Mitsubishi Chemical Co., Ltd.) was added so that the solid content concentration was 20% by mass, the reaction system internal temperature was cooled to 100° C. got varnish.

Subsequently, on a glass plate, the obtained polyimide varnish is applied by spin coating, held on a hot plate at 80° C. for 20 minutes, and then heated in an air atmosphere at 260° C. in a hot air dryer for 30 minutes to evaporate the solvent. , a film was obtained. A result is shown in Table 1.

<Example 6>

26.505 g (0.106 mol) of 3,3'-DDS was added to a 300 mL 5-neck round-bottom flask equipped with a stainless steel semi-lunar stirring blade, a nitrogen introduction tube, a Dean-Stark with a cooling tube, a thermometer, and a glass end cap; 8.513 g (0.027 mol) of TFMB and 63.345 g of γ-butyrolactone (manufactured by Mitsubishi Chemical Co., Ltd.) were added, followed by stirring at a system temperature of 70° C., a nitrogen atmosphere, and a rotation speed of 200 rpm to obtain a solution.

To this solution, 29.768 g (0.133 mol) of HPMDA and 15.836 g of γ-butyrolactone (manufactured by Mitsubishi Chemical Co., Ltd.) were added at once, followed by 0.672 triethylamine (manufactured by Kanto Chemical Co., Ltd.) as an imidization catalyst. g was added, heated with a mantle heater, and the internal temperature of the reaction system was raised to 190°C over about 20 minutes. The components being distilled were collected, and while the number of rotations was adjusted according to the increase in viscosity, the temperature in the reaction system was maintained at 190° C. and refluxed for 5 hours.

Thereafter, 160.819 g of γ-butyrolactone (manufactured by Mitsubishi Chemical Co., Ltd.) was added so that the solid content concentration was 20% by mass, the temperature inside the reaction system was cooled to 100° C. got varnish.

Subsequently, on a glass plate, the obtained polyimide varnish is applied by spin coating, held on a hot plate at 80° C. for 20 minutes, and then heated at 260° C. in an air atmosphere for 30 minutes in a hot air dryer to evaporate the solvent. , a film was obtained. A result is shown in Table 1.

<Comparative Example 1>

28.588 g (0.115 mol) of 3,3'-DDS was added to a 300 mL 5-necked round-bottom flask equipped with a stainless steel semi-lunar stirring blade, a nitrogen introduction tube, a Dean-Stark with a cooling tube, a thermometer, and a glass end cap; 62.704 g of γ-butyrolactone (manufactured by Mitsubishi Chemical Co., Ltd.) was added and stirred at a system internal temperature of 70° C., a nitrogen atmosphere, and a rotation speed of 200 rpm to obtain a solution.

To this solution, 35.541 g (0.115 mol) of ODPA and 15.676 g of γ-butyrolactone (manufactured by Mitsubishi Chemical Co., Ltd.) were added at once, followed by 0.580 triethylamine (manufactured by Kanto Chemical Co., Ltd.) as an imidization catalyst. g was added, heated with a mantle heater, and the internal temperature of the reaction system was raised to 190°C over about 20 minutes. The components being distilled were collected, and while the number of rotations was adjusted according to the increase in viscosity, the temperature in the reaction system was maintained at 190° C. and refluxed for 5 hours.

Then, 161.620 g of γ-butyrolactone (manufactured by Mitsubishi Chemical Co., Ltd.) was added so that the solid content concentration was 20% by mass, and the reaction system internal temperature was cooled to 100° C. got varnish.

Subsequently, on a glass plate, the obtained polyimide varnish is applied by spin coating, held on a hot plate at 80° C. for 20 minutes, and then heated in an air atmosphere at 260° C. in a hot air dryer for 30 minutes to evaporate the solvent. , a film was obtained. A result is shown in Table 1.

<Comparative Example 2>

15.901 g (0.064 mol) of 3,3'-DDS was added to a 300 mL 5-neck round-bottom flask equipped with a stainless steel semi-lunar stirring blade, a nitrogen introduction tube, a Dean-Stark with a cooling tube, a thermometer, and a glass end cap; 9.156 g (0.064 mol) of 1,3-BAC and 63.157 g of γ-butyrolactone (manufactured by Mitsubishi Chemical Co., Ltd.) were added, and stirred at a system temperature of 70° C., nitrogen atmosphere, and rotation speed 200 rpm to obtain a solution.

To this solution, 39.536 g (0.127 mol) of ODPA and 15.789 g of γ-butyrolactone (manufactured by Mitsubishi Chemical Co., Ltd.) were added in a batch, followed by 0.967 triethylamine (manufactured by Kanto Chemical Co., Ltd.) as an imidization catalyst. g was added, heated with a mantle heater, and the internal temperature of the reaction system was raised to 190°C over about 20 minutes. The components being distilled were collected, and while the number of rotations was adjusted according to the increase in viscosity, the temperature in the reaction system was maintained at 190° C. and refluxed for 5 hours.

Then, 159.801 g of γ-butyrolactone (manufactured by Mitsubishi Chemical Co., Ltd.) was added so that the solid content concentration was 20% by mass, and the reaction system internal temperature was cooled to 100° C. got varnish.

Subsequently, on a glass plate, the obtained polyimide varnish is applied by spin coating, held on a hot plate at 80° C. for 20 minutes, and then heated in an air atmosphere at 260° C. in a hot air dryer for 30 minutes to evaporate the solvent. , a film was obtained. A result is shown in Table 1.

<Comparative Example 3>

13.053 g (0.052 mol) of 3,3'-DDS in a 300 mL 5-neck round-bottom flask equipped with a stainless steel semi-lunar stirring blade, a nitrogen introduction tube, a Dean-Stark with a cooling tube, a thermometer, and a glass end cap, 18.263 g (0.052 mol) of BAFL and 62.353 g of γ-butyrolactone (manufactured by Mitsubishi Chemical Co., Ltd.) were added, and stirred at a system temperature of 70° C., nitrogen atmosphere, and rotation speed 200 rpm to obtain a solution.

To this solution, 32.455 g (0.105 mol) of ODPA and 15.588 g of γ-butyrolactone (manufactured by Mitsubishi Chemical Co., Ltd.) were added at once, followed by 0.529 triethylamine (manufactured by Kanto Chemical Co., Ltd.) as an imidization catalyst. g was added, heated with a mantle heater, and the internal temperature of the reaction system was raised to 190°C over about 20 minutes. The components being distilled were collected, and while the number of rotations was adjusted according to the increase in viscosity, the temperature in the reaction system was maintained at 190° C. and refluxed for 5 hours.

Then, 162.059 g of γ-butyrolactone (manufactured by Mitsubishi Chemical Co., Ltd.) was added so that the solid content concentration was 20% by mass, and the temperature inside the reaction system was cooled to 100° C. got varnish.

Subsequently, on a glass plate, the obtained polyimide varnish is applied by spin coating, held on a hot plate at 80° C. for 20 minutes, and then heated in an air atmosphere at 260° C. in a hot air dryer for 30 minutes to evaporate the solvent. , a film was obtained. A result is shown in Table 1.

<Comparative Example 4>

28.535 g (0.115 mol) of 4,4'-DDS, 28.535 g (0.115 mol) of 4,4'-DDS in a 300 mL 5-neck round-bottom flask equipped with a stainless steel semi-lunar stirring blade, a nitrogen inlet tube, a Dean-Stark with a cooling tube, a thermometer, and a glass end cap. - 62.710 g of butyrolactone (manufactured by Mitsubishi Chemical Co., Ltd.) was added, and stirred at a system temperature of 70° C., a nitrogen atmosphere, and a rotation speed of 200 rpm to obtain a solution.

To this solution, 35.600 g (0.115 mol) of ODPA and 15.678 g of γ-butyrolactone (manufactured by Mitsubishi Chemical Co., Ltd.) were added at once, followed by 0.581 triethylamine (manufactured by Kanto Chemical Co., Ltd.) as an imidization catalyst. g, and as a result of heating with a mantle heater, the reaction solution became cloudy and no varnish could be obtained.

<Comparative Example 5>

34.192 g (0.137 mol) of 3,3'-DDS was added to a 300 mL 5-neck round-bottom flask equipped with a stainless steel semi-lunar stirring blade, a nitrogen introduction tube, a Dean-Stark with a cooling tube, a thermometer, and a glass end cap; 63.495 g of γ-butyrolactone (manufactured by Mitsubishi Chemical Co., Ltd.) was added, and stirred at a system temperature of 70° C., a nitrogen atmosphere, and a rotation speed of 200 rpm to obtain a solution.

To this solution, 30.746 g (0.137 mol) of HPMDA and 15.874 g of γ-butyrolactone (manufactured by Mitsubishi Chemical Co., Ltd.) were added at once, followed by 0.693 triethylamine (manufactured by Kanto Chemical Co., Ltd.) as an imidization catalyst. g was added, heated with a mantle heater, and the internal temperature of the reaction system was raised to 190°C over about 20 minutes. The components to be distilled were collected, and while the number of rotations was adjusted according to the increase in viscosity, the temperature in the reaction system was maintained at 190° C. and refluxed for 5 hours.

Thereafter, 160.631 g of γ-butyrolactone (manufactured by Mitsubishi Chemical Co., Ltd.) was added so that the solid content concentration was 20% by mass, and the reaction system internal temperature was cooled to 100° C. got varnish.

Subsequently, on a glass plate, the obtained polyimide varnish is applied by spin coating, held on a hot plate at 80° C. for 20 minutes, and then heated in an air atmosphere at 260° C. in a hot air dryer for 30 minutes to evaporate the solvent. , a film was obtained. A result is shown in Table 1.

<Comparative Example 6>

15.819 g (0.063 mol) of 3,3'-DDS was added to a 300 mL 5-neck round-bottom flask equipped with a stainless steel semi-lunar stirring blade, nitrogen inlet tube, Dean-Stark with cooling tube, thermometer, and glass end cap, 20.323 g (0.063 mol) of TFMB and 63.134 g of γ-butyrolactone (manufactured by Mitsubishi Chemical Co., Ltd.) were added and stirred at a system temperature of 70° C., nitrogen atmosphere, and rotation speed 200 rpm to obtain a solution.

To this solution, 28.427 g (0.127 mol) of HPMDA and 15.784 g of γ-butyrolactone (manufactured by Mitsubishi Chemical Co., Ltd.) were added at once, followed by 0.641 triethylamine (manufactured by Kanto Chemical Co., Ltd.) as an imidization catalyst. g was added, heated with a mantle heater, and the internal temperature of the reaction system was raised to 190°C over about 20 minutes. The components being distilled were collected, and while the number of rotations was adjusted according to the increase in viscosity, the temperature in the reaction system was maintained at 190° C. and refluxed for 5 hours.

Thereafter, 161.082 g of γ-butyrolactone (manufactured by Mitsubishi Chemical Co., Ltd.) was added so that the solid content concentration was 20% by mass, and the reaction system internal temperature was cooled to 100° C. got varnish.

Subsequently, on a glass plate, the obtained polyimide varnish is applied by spin coating, held on a hot plate at 80° C. for 20 minutes, and then heated in an air atmosphere at 260° C. in a hot air dryer for 30 minutes to evaporate the solvent. , a film was obtained. A result is shown in Table 1.

<Comparative Example 7>

15.356 g (0.062 mol) of 3,3'-DDS was added to a 300 mL 5-neck round-bottom flask equipped with a stainless steel semi-lunar stirring blade, nitrogen introduction tube, cooling tube attached Dean-Stark, thermometer, and glass end cap; 21.485 g (0.062 mol) of BAFL, and 63.004 g of γ-butyrolactone (manufactured by Mitsubishi Chemical Co., Ltd.) were added, and stirred at a system temperature of 70° C., nitrogen atmosphere, and rotation speed 200 rpm to obtain a solution.

To this solution, 27.594 g (0.123 mol) of HPMDA and 15.751 g of γ-butyrolactone (manufactured by Mitsubishi Chemical Co., Ltd.) were added at once, followed by 0.623 triethylamine (manufactured by Kanto Chemical Co., Ltd.) as an imidization catalyst. g was added, heated with a mantle heater, and the internal temperature of the reaction system was raised to 190°C over about 20 minutes. The components being distilled were collected, and while the number of rotations was adjusted according to the increase in viscosity, the temperature in the reaction system was maintained at 190° C. and refluxed for 5 hours.

Thereafter, 161.246 g of γ-butyrolactone (manufactured by Mitsubishi Chemical Co., Ltd.) was added so that the solid content concentration was 20% by mass, the temperature inside the reaction system was cooled to 100° C. got varnish.

Subsequently, on a glass plate, the obtained polyimide varnish is applied by spin coating, held on a hot plate at 80° C. for 20 minutes, and then heated in an air atmosphere at 260° C. in a hot air dryer for 30 minutes to evaporate the solvent. , a film was obtained. A result is shown in Table 1.

<Comparative Example 8>

34.155 g (0.137 mol) of 4,4'-DDS was added to a 300 mL 5-neck round-bottom flask equipped with a stainless steel semi-lunar stirring blade, a nitrogen introduction tube, a Dean-Stark with a cooling tube, a thermometer, and a glass end cap, 63.507 g of γ-butyrolactone (manufactured by Mitsubishi Chemical Co., Ltd.) was added, and stirred at a system internal temperature of 70° C., a nitrogen atmosphere, and a rotation speed of 200 rpm to obtain a solution.

To this solution, 30.795 g (0.137 mol) of HPMDA and 15.877 g of γ-butyrolactone (manufactured by Mitsubishi Chemical Co., Ltd.) were added at once, followed by 0.695 triethylamine (manufactured by Kanto Chemical Co., Ltd.) as an imidization catalyst. g was added, and as a result of heating with a mantle heater, the reaction solution became cloudy and a varnish could not be obtained.

<Example 7>

23.921 g (0.096 mol) of 3,3'-DDS was added to a 300 mL 5-neck round-bottom flask equipped with a stainless steel semi-lunar stirring blade, a nitrogen introduction tube, a Dean-Stark with a cooling tube, a thermometer, and a glass end cap; 8.367 g (0.024 mol) of BAFL, and 62.889 g of γ-butyrolactone (manufactured by Mitsubishi Chemical Co., Ltd.) were added, and stirred at a system temperature of 70° C., nitrogen atmosphere, and rotation speed 200 rpm to obtain a solution.

To this solution, 13.444 g (0.060 mol) of HPMDA, 18.587 g (0.060 mol) of ODPA, and 15.722 g of γ-butyrolactone (manufactured by Mitsubishi Chemical Co., Ltd.) were added at once, followed by tri-imidization catalyst. 0.606 g of ethylamine (manufactured by Kanto Chemical Co., Ltd.) was added, heated with a mantle heater, and the internal temperature of the reaction system was raised to 190°C over about 20 minutes. The components being distilled were collected, and while the number of rotations was adjusted according to the increase in viscosity, the temperature in the reaction system was maintained at 190° C. and refluxed for 5 hours.

Thereafter, 161.389 g of γ-butyrolactone (manufactured by Mitsubishi Chemical Co., Ltd.) was added so that the solid content concentration was 20% by mass, the temperature inside the reaction system was cooled to 100° C. got varnish.

Subsequently, on a glass plate, the obtained polyimide varnish is applied by spin coating, held on a hot plate at 80° C. for 20 minutes, and then heated in an air atmosphere at 260° C. in a hot air dryer for 30 minutes to evaporate the solvent. , a film was obtained. A result is shown in Table 2.

<Example 8>

22.397 g (0.090 mol) of 3,3'-DDS was added to a 300 mL 5-neck round-bottom flask equipped with a stainless steel semi-lunar stirring blade, a nitrogen introduction tube, a Dean-Stark with a cooling tube, a thermometer, and a glass end cap; 11.657 g (0.022 mol) of HFBAPP and 62.620 g of γ-butyrolactone (manufactured by Mitsubishi Chemical Co., Ltd.) were added, followed by stirring at a system temperature of 70° C., a nitrogen atmosphere, and a rotation speed of 200 rpm to obtain a solution.

To this solution, 12.587 g (0.056 mol) of HPMDA, 17.402 g (0.056 mol) of ODPA, and 15.655 g of γ-butyrolactone (manufactured by Mitsubishi Chemical Co., Ltd.) were added at once, followed by tri-imidization catalyst. 0.568 g of ethylamine (manufactured by Kanto Chemical Co., Ltd.) was added, heated with a mantle heater, and the internal temperature of the reaction system was raised to 190°C over about 20 minutes. The components being distilled were collected, and while the number of rotations was adjusted according to the increase in viscosity, the temperature in the reaction system was maintained at 190° C. and refluxed for 5 hours.

Thereafter, 161.725 g of γ-butyrolactone (manufactured by Mitsubishi Chemical Co., Ltd.) was added so that the solid content concentration was 20% by mass, and the reaction system internal temperature was cooled to 100° C. got varnish.

Subsequently, on a glass plate, the obtained polyimide varnish is applied by spin coating, held on a hot plate at 80° C. for 20 minutes, and then heated in an air atmosphere at 260° C. in a hot air dryer for 30 minutes to evaporate the solvent. , a film was obtained. A result is shown in Table 2.

<Example 9>

24.042 g (0.096 mol) of 3,3'-DDS in a 300 mL 5-neck round-bottom flask equipped with a stainless steel half-moon stirring blade, nitrogen inlet tube, Dean-Stark with cooling tube, thermometer, and glass end cap, 8.106 g (0.024 mol) of 6FODA and 62.910 g of γ-butyrolactone (manufactured by Mitsubishi Chemical Co., Ltd.) were added, followed by stirring at a system temperature of 70° C., a nitrogen atmosphere, and a rotation speed of 200 rpm to obtain a solution.

To this solution, 13.512 g (0.060 mol) of HPMDA, 18.681 g (0.060 mol) of ODPA, and 15.728 g of γ-butyrolactone (manufactured by Mitsubishi Chemical Co., Ltd.) were added at once, followed by tri- as an imidization catalyst. 0.609 g of ethylamine (manufactured by Kanto Chemical Co., Ltd.) was added, heated with a mantle heater, and the internal temperature of the reaction system was raised to 190°C over about 20 minutes. The components being distilled were collected, and while the number of rotations was adjusted according to the increase in viscosity, the temperature in the reaction system was maintained at 190° C. and refluxed for 5 hours.

Thereafter, 161.362 g of γ-butyrolactone (manufactured by Mitsubishi Chemical Co., Ltd.) was added so that the solid content concentration was 20% by mass, and the reaction system internal temperature was cooled to 100° C. got varnish.

Subsequently, on a glass plate, the obtained polyimide varnish is applied by spin coating, held on a hot plate at 80° C. for 20 minutes, and then heated in an air atmosphere at 260° C. in a hot air dryer for 30 minutes to evaporate the solvent. , a film was obtained. A result is shown in Table 2.

<Example 10>

25.353 g (0.102 mol) of 3,3'-DDS in a 300 mL 5-neck round-bottom flask equipped with a stainless steel semi-lunar stirring blade, a nitrogen introduction tube, a Dean-Stark with a cooling tube, a thermometer, and a glass end cap, 8.547 g (0.025 mol) of 6FODA and 63.142 g of γ-butyrolactone (manufactured by Mitsubishi Chemical Co., Ltd.) were added, and stirred at a system temperature of 70° C., nitrogen atmosphere, and rotation speed 200 rpm to obtain a solution.

To this solution, 22.797 g (0.102 mol) of HPMDA, 7.880 g (0.025 mol) of ODPA, and 15.785 g of γ-butyrolactone (manufactured by Mitsubishi Chemical Co., Ltd.) were added at once, followed by tri-imidization catalyst. 0.643 g of ethylamine (manufactured by Kanto Chemical Co., Ltd.) was added, heated with a mantle heater, and the internal temperature of the reaction system was raised to 190°C over about 20 minutes. The components being distilled were collected, and while the number of rotations was adjusted according to the increase in viscosity, the temperature in the reaction system was maintained at 190° C. and refluxed for 5 hours.

Thereafter, 161.073 g of γ-butyrolactone (manufactured by Mitsubishi Chemical Co., Ltd.) was added so that the solid content concentration was 20% by mass, and the reaction system internal temperature was cooled to 100° C. got varnish.

Subsequently, on a glass plate, the obtained polyimide varnish is applied by spin coating, held on a hot plate at 80° C. for 20 minutes, and then heated in an air atmosphere at 260° C. in a hot air dryer for 30 minutes to evaporate the solvent. , a film was obtained. A result is shown in Table 2.

<Example 11>

23.530 g (0.094 mol) of 3,3'-DDS was added to a 300 mL 5-neck round-bottom flask equipped with a stainless steel semi-lunar stirring blade, a nitrogen inlet tube, a Dean-Stark with a cooling tube, a thermometer, and a glass end cap; 12.247 g (0.024 mol) of HFBAPP and 62.820 g of γ-butyrolactone (manufactured by Mitsubishi Chemical Co., Ltd.) were added, and stirred at a system temperature of 70° C., nitrogen atmosphere, and rotation speed 200 rpm to obtain a solution.

To this solution, 21.158 g (0.094 mol) of HPMDA, 7.313 g (0.024 mol) of ODPA, and 15.705 g of γ-butyrolactone (manufactured by Mitsubishi Chemical Co., Ltd.) were added at once, followed by tri-imidization catalyst. 0.596 g of ethylamine (manufactured by Kanto Chemical Co., Ltd.) was added, heated with a mantle heater, and the internal temperature of the reaction system was raised to 190°C over about 20 minutes. The components being distilled were collected, and while the number of rotations was adjusted according to the increase in viscosity, the temperature in the reaction system was maintained at 190° C. and refluxed for 5 hours.

Thereafter, 161.475 g of γ-butyrolactone (manufactured by Mitsubishi Chemical Co., Ltd.) is added so that the solid content concentration is 20% by mass, the temperature inside the reaction system is cooled to 100° C. got varnish.

Subsequently, on a glass plate, the obtained polyimide varnish is applied by spin coating, held on a hot plate at 80° C. for 20 minutes, and then heated in an air atmosphere at 260° C. in a hot air dryer for 30 minutes to evaporate the solvent. , a film was obtained. A result is shown in Table 2.

<Example 12>

25.218 g (0.101 mol) of 3,3'-DDS was added to a 300 mL 5-neck round-bottom flask equipped with a stainless steel semi-lunar stirring blade, a nitrogen introduction tube, a Dean-Stark with a cooling tube, a thermometer, and a glass end cap; 8.821 g (0.025 mol) of BAFL and 63.118 g of γ-butyrolactone (manufactured by Mitsubishi Chemical Co., Ltd.) were added, and stirred at a system temperature of 70° C., nitrogen atmosphere, and rotation speed 200 rpm to obtain a solution.

To this solution, 22.676 g (0.101 mol) of HPMDA, 7.838 g (0.025 mol) of ODPA, and 15.780 g of γ-butyrolactone (manufactured by Mitsubishi Chemical Co., Ltd.) were added at once, followed by tri- as an imidization catalyst. 0.639 g of ethylamine (manufactured by Kanto Chemical Co., Ltd.) was added, heated with a mantle heater, and the internal temperature of the reaction system was raised to 190°C over about 20 minutes. The components being distilled were collected, and while the number of rotations was adjusted according to the increase in viscosity, the temperature in the reaction system was maintained at 190° C. and refluxed for 5 hours.

Thereafter, 161.102 g of γ-butyrolactone (manufactured by Mitsubishi Chemical Co., Ltd.) was added so that the solid content concentration was 20% by mass, the temperature inside the reaction system was cooled to 100° C. got varnish.

Subsequently, on a glass plate, the obtained polyimide varnish is applied by spin coating, held on a hot plate at 80° C. for 20 minutes, and then heated in an air atmosphere at 260° C. in a hot air dryer for 30 minutes to evaporate the solvent. , a film was obtained. A result is shown in Table 2.

<Example 13>

23.933 g (0.096 mol) of 3,3'-DDS was added to a 300 mL 5-necked round-bottom flask equipped with a stainless steel semi-lunar stirring blade, a nitrogen introduction tube, a Dean-Stark with a cooling tube, a thermometer, and a glass end cap; 12.457 g (0.024 mol) of HFBAPP and 62.891 g of γ-butyrolactone (manufactured by Mitsubishi Chemical Co., Ltd.) were added, and stirred at a system temperature of 70° C., nitrogen atmosphere, and rotation speed 200 rpm to obtain a solution.

To this solution, 24.211 g (0.108 mol) of HPMDA, 3.719 g (0.012 mol) of ODPA, and 15.723 g of γ-butyrolactone (manufactured by Mitsubishi Chemical Co., Ltd.) were added at once, followed by tri-imidization catalyst. 0.607 g of ethylamine (manufactured by Kanto Chemical Co., Ltd.) was added, heated with a mantle heater, and the internal temperature of the reaction system was raised to 190°C over about 20 minutes. The components being distilled were collected, and while the number of rotations was adjusted according to the increase in viscosity, the temperature in the reaction system was maintained at 190° C. and refluxed for 5 hours.

Thereafter, 161.386 g of γ-butyrolactone (manufactured by Mitsubishi Chemical Co., Ltd.) was added so that the solid content concentration was 20% by mass, and the temperature inside the reaction system was cooled to 100° C. got varnish.

Subsequently, on a glass plate, the obtained polyimide varnish is applied by spin coating, held on a hot plate at 80° C. for 20 minutes, and then heated in an air atmosphere at 260° C. in a hot air dryer for 30 minutes to evaporate the solvent. , a film was obtained. A result is shown in Table 2.

<Example 14>

25.822 g (0.103 mol) of 3,3'-DDS was added to a 300 mL 5-neck round-bottom flask equipped with a stainless steel semi-lunar stirring blade, a nitrogen introduction tube, a Dean-Stark with a cooling tube, a thermometer, and a glass end cap, 8.706 g (0.026 mol) of 6FODA and 63.225 g of γ-butyrolactone (manufactured by Mitsubishi Chemical Co., Ltd.) were added, and stirred at a system temperature of 70° C., nitrogen atmosphere, and rotation speed 200 rpm to obtain a solution.

To this solution, 26.121 g (0.116 mol) of HPMDA, 4.013 g (0.013 mol) of ODPA, and 15.806 g of γ-butyrolactone (manufactured by Mitsubishi Chemical Co., Ltd.) were added at once, followed by tri- as an imidization catalyst. 0.654 g of ethylamine (manufactured by Kanto Chemical Co., Ltd.) was added, heated with a mantle heater, and the reaction system internal temperature was raised to 190°C over about 20 minutes. The components being distilled were collected, and while the number of rotations was adjusted according to the increase in viscosity, the temperature in the reaction system was maintained at 190° C. and refluxed for 5 hours.

Thereafter, 160.969 g of γ-butyrolactone (manufactured by Mitsubishi Chemical Co., Ltd.) is added so that the solid content concentration is 20% by mass, the temperature inside the reaction system is cooled to 100° C. got varnish.

Subsequently, on a glass plate, the obtained polyimide varnish is applied by spin coating, held on a hot plate at 80° C. for 20 minutes, and then heated in an air atmosphere at 260° C. in a hot air dryer for 30 minutes to evaporate the solvent. , a film was obtained. A result is shown in Table 2.

<Example 15>

26.000 g (0.104 mol) of 3,3'-DDS was added to a 300 mL 5-neck round-bottom flask equipped with a stainless steel semi-lunar stirring blade, a nitrogen introduction tube, a Dean-Stark with a cooling tube, a thermometer, and a glass end cap; 8.351 g (0.026 mol) of TFMB and 63.256 g of γ-butyrolactone (manufactured by Mitsubishi Chemical Co., Ltd.) were added, and stirred at a system temperature of 70° C., nitrogen atmosphere, and rotation speed 200 rpm to obtain a solution.

To this solution, 26.302 g (0.117 mol) of HPMDA, 4.041 g (0.013 mol) of ODPA, and 15.814 g of γ-butyrolactone (manufactured by Mitsubishi Chemical Co., Ltd.) were added at once, followed by tri- as an imidization catalyst. 0.659 g of ethylamine (manufactured by Kanto Chemical Co., Ltd.) was added, heated with a mantle heater, and the internal temperature of the reaction system was raised to 190°C over about 20 minutes. The components being distilled were collected, and while the number of rotations was adjusted according to the increase in viscosity, the temperature in the reaction system was maintained at 190° C. and refluxed for 5 hours.

Thereafter, 160.930 g of γ-butyrolactone (manufactured by Mitsubishi Chemical Co., Ltd.) was added so that the solid content concentration was 20% by mass, and the reaction system internal temperature was cooled to 100° C. got varnish.

Subsequently, on a glass plate, the obtained polyimide varnish is applied by spin coating, held on a hot plate at 80° C. for 20 minutes, and then heated in an air atmosphere at 260° C. in a hot air dryer for 30 minutes to evaporate the solvent. , a film was obtained. A result is shown in Table 2.

<Comparative Example 9>

36.092 g (0.103 mol) of BAFL and γ-butyrolactone in a 300 mL 5-neck round-bottom flask equipped with a stainless steel semi-lunar stirring blade, a nitrogen introduction tube, a Dean-Stark with a cooling tube, a thermometer, and a glass end cap. 63.309 g (manufactured by Mitsubishi Chemical Co., Ltd.) was added, and the mixture was stirred at a system internal temperature of 70° C., a nitrogen atmosphere, and a rotational speed of 200 rpm to obtain a solution.

To this solution, 11.598 g (0.052 mol) of HPMDA, 16.035 g (0.052 mol) of ODPA, and 15.577 g of γ-butyrolactone (manufactured by Mitsubishi Chemical Co., Ltd.) were added at once, followed by tri- as an imidization catalyst. 0.523 g of ethylamine (manufactured by Kanto Chemical Co., Ltd.) was added, heated with a mantle heater, and the internal temperature of the reaction system was raised to 190°C over about 20 minutes. The components being distilled were collected, and while the number of rotations was adjusted according to the increase in viscosity, the temperature in the reaction system was maintained at 190° C. and refluxed for 5 hours.

Thereafter, 162.113 g of γ-butyrolactone (manufactured by Mitsubishi Chemical Co., Ltd.) was added so that the solid content concentration was 20% by mass, and the temperature inside the reaction system was cooled to 100° C. got varnish.

Subsequently, on a glass plate, the obtained polyimide varnish is applied by spin coating, held on a hot plate at 80° C. for 20 minutes, and then heated in an air atmosphere at 260° C. in a hot air dryer for 30 minutes to evaporate the solvent. , a film was obtained. A result is shown in Table 2.

<Comparative Example 10>

14.109 g (0.057 mol) of 3,3'-DDS was added to a 300 mL 5-neck round-bottom flask equipped with a stainless steel semi-lunar stirring blade, a nitrogen introduction tube, a Dean-Stark with a cooling tube, a thermometer, and a glass end cap; 19.740 g (0.057 mol) of BAFL and 62.651 g of γ-butyrolactone (manufactured by Mitsubishi Chemical Co., Ltd.) were added, and stirred at a system temperature of 70° C., nitrogen atmosphere, and rotation speed 200 rpm to obtain a solution.

To this solution, 12.687 g (0.057 mol) of HPMDA, 17.540 g (0.057 mol) of ODPA, and 15.663 g of γ-butyrolactone (manufactured by Mitsubishi Chemical Co., Ltd.) were added at once, followed by tri- as an imidization catalyst. 0.572 g of ethylamine (manufactured by Kanto Chemical Co., Ltd.) was added, heated with a mantle heater, and the internal temperature of the reaction system was raised to 190°C over about 20 minutes. The components being distilled were collected, and while the number of rotations was adjusted according to the increase in viscosity, the temperature in the reaction system was maintained at 190° C. and refluxed for 5 hours.

Thereafter, 161.686 g of γ-butyrolactone (manufactured by Mitsubishi Chemical Co., Ltd.) was added so that the solid content concentration was 20% by mass, and the reaction system internal temperature was cooled to 100° C. got varnish.

Subsequently, on a glass plate, the obtained polyimide varnish is applied by spin coating, held on a hot plate at 80° C. for 20 minutes, and then heated in an air atmosphere at 260° C. in a hot air dryer for 30 minutes to evaporate the solvent. , a film was obtained. A result is shown in Table 2.

[Table 1]

On the other hand, in Comparative Examples 4 and 8, the reaction solution became cloudy during synthesis of the polyimide resin, and a varnish could not be obtained. Therefore, the physical properties of the film could not be measured.

In addition, since the film of Comparative Example 5 deteriorated remarkably as a result of being immersed in a mixed acid in an acid resistance test, YI and b ^* after immersion could not be measured. Therefore, ΔYI and Δb ^* of Comparative Example 5 could not be obtained.

[Table 2]

As shown in Table 1, the polyimide films of Examples 1 to 6 used HPMDA or ODPA as a tetracarboxylic acid component, and 3,3'-DDS and a specific second diamine (6FODA, BAFL, HFBAPP, X-22-9409, or TFMB). As a result, colorless transparency, optical isotropy, and chemical resistance (solvent resistance, acid resistance and alkali resistance) were excellent.

On the other hand, in Comparative Examples 1-4, although ODPA was used as a tetracarboxylic acid component, a diamine component was not made into the structure of this invention. The polyimide film of Comparative Example 1 prepared using only 3,3'-DDS as the diamine component was inferior in colorless transparency and optical isotropy. The polyimide film of Comparative Example 2 produced by using together 3,3'-DDS and a diamine (1,3-BAC) other than the specific second diamine as a diamine component was inferior in solvent resistance. Although it was prepared by using 3,3'-DDS and a specific second diamine (BAFL) as a diamine component in combination, the polyimide film of Comparative Example 3 in which the ratio of 3,3'-DDS was less than 70 mol% was colorless and transparent (total light). transmittance), optical isotropy and acid resistance. In Comparative Example 4 using 4,4'-DDS as the diamine component, the reaction solution became cloudy during synthesis of the polyimide resin, and varnish could not be obtained.

In Comparative Examples 5 to 8, HPMDA was used as the tetracarboxylic acid component, but the diamine component was not constituted of the present invention. The polyimide film of Comparative Example 5 prepared using only 3,3'-DDS as the diamine component had poor acid resistance. Although 3,3'-DDS and a specific second diamine (TFMB) were used together as a diamine component, the polyimide film of Comparative Example 6 in which the ratio of 3,3'-DDS was less than 70 mol% had poor solvent resistance. lost. Although 3,3'-DDS and a specific secondary diamine (BAFL) were used together as a diamine component, the polyimide film of Comparative Example 7 in which the ratio of 3,3'-DDS was less than 70 mol% was inferior in acid resistance. . In Comparative Example 8 using 4,4'-DDS as the diamine component, the reaction solution became cloudy during synthesis of the polyimide resin, and varnish could not be obtained.

In addition, as shown in Table 2, the polyimide films of Examples 7 to 15 prepared by using HPMDA and ODPA as tetracarboxylic acid components in combination were also colorless and transparent, optically isotropic, and chemical resistance (solvent resistance, acid resistance and alkali resistance) ) was excellent.

On the other hand, in Comparative Examples 9 and 10, HPMDA and ODPA were used together as the tetracarboxylic acid component, but the diamine component was not constituted of the present invention. The polyimide film of Comparative Example 9 prepared using only BAFL as the diamine component was inferior in acid resistance. Although 3,3'-DDS and a specific secondary diamine (BAFL) were used together as a diamine component, the polyimide film of Comparative Example 10 in which the ratio of 3,3'-DDS was less than 70 mol% was optically isotropic and acid-resistant this fell behind

Claims (10)

A polyimide resin having a structural unit A derived from tetracarboxylic dianhydride and a structural unit B derived from diamine,
The structural unit A is a structural unit (A-1-1) derived from a compound represented by the following formula (a-1-1) and a structural unit (A) derived from a compound represented by the following formula (a-1-2) It contains at least one structural unit (A-1) selected from the group consisting of -1,2),
The structural unit B is a structural unit derived from a compound represented by the following formula (b-1) (B-1), and a structural unit derived from a compound represented by the following formula (b-2-1) (B-2-) 1), a structural unit derived from a compound represented by the following formula (b-2-2) (B-2-2), a structural unit derived from a compound represented by the following formula (b-2-3) (B- 2-3), a structural unit derived from a compound represented by the following formula (b-2-4) (B-2-4), and a structural unit derived from a compound represented by the following formula (b-2-5) (B-2-5) comprising at least one structural unit (B-2) selected from the group consisting of,
The polyimide resin whose ratio of the structural unit (B-1) in structural unit B is 70 mol% or more.
[Formula 1]

(in formula (b-2-2),
R is each independently a hydrogen atom, a fluorine atom or a methyl group,
In formula (b-2-4),
R ¹ to R ⁴ are each independently a monovalent aliphatic group or a monovalent aromatic group,
Z ¹ and Z ² are each independently a divalent aliphatic group or a divalent aromatic group,
r is a positive integer.) According to claim 1,
The proportion of the structural unit (B-1) in the structural unit B is 70 to 97 mol%,
The polyimide resin whose ratio of the structural unit (B-2) in structural unit B is 3-30 mol%. 3. The method of claim 1 or 2,
The polyimide resin whose ratio of the structural unit (A-1) in structural unit A is 50 mol% or more. 4. The method according to any one of claims 1 to 3,
The polyimide resin whose structural unit (B-2) is a structural unit (B-2-1). 4. The method according to any one of claims 1 to 3,
A polyimide resin whose structural unit (B-2) is a structural unit (B-2-2). 4. The method according to any one of claims 1 to 3,
The structural unit (B-2) is a structural unit (B-2-3), polyimide resin. 4. The method according to any one of claims 1 to 3,
A polyimide resin whose structural unit (B-2) is a structural unit (B-2-4). 4. The method according to any one of claims 1 to 3,
The structural unit (B-2) is a structural unit (B-2-5), polyimide resin. A polyimide varnish in which the polyimide resin according to any one of claims 1 to 8 is dissolved in an organic solvent. The polyimide film containing the polyimide resin in any one of Claims 1-8.