TW202302713A - Polyimide resin composition, polyimide precursor composition, varnish, and polyimide film - Google Patents

Abstract

A polyimide resin composition that includes a polyimide having a repeating unit represented by general formula (1) shown below, and at least one compound selected from the group consisting of compounds represented by general formulas (2-1), (2-2), (2-3) and (2-4) shown below. (In the formulas, X1 represents a tetravalent group having an alicyclic structure or aromatic ring having at least one norbornane skeleton, X represents a single bond, -HNCO-, -CONH-, -COO- or -OCO-, R1 and R2 each represent a hydrogen atom, an alkyl group of 1 to 6 carbon atoms, a phenyl group, or an aminoalkyl group of 1 to 6 carbon atoms, and R3 represents an alkyl group of 1 to 6 carbon atoms.).

Description

Polyimide resin composition, polyimide precursor composition, varnish, and polyimide film

The present invention relates to a polyimide resin composition, a polyimide precursor composition, a varnish, and a polyimide film.

Polyimide resin has excellent mechanical properties and heat resistance, so it is being studied for various uses in fields such as electrical and electronic parts. For example, it is desired to replace glass substrates used in image display devices such as liquid crystal displays and OLED displays with polyimide film substrates. Therefore, polyimide resins satisfying the performance as optical materials are being developed. However, in recent years, due to the high functionality of electronic equipment, electronic parts must simultaneously satisfy various required performances. Therefore, some people also mix various additives in the polyimide resin used in the display to add new properties to the original properties of the resin or try to improve the original properties.

For example, Patent Document 1 discloses a polyimide precursor containing a structural unit derived from 2,2'-bis(trifluoromethyl)benzidine, a polysiloxane-based interfacial Resin composition of active agent and organic solvent. In addition, Patent Document 2 discloses polyimide containing 5% of polyimide with a thermal decomposition temperature of 350° C. or higher, and polyimide having a functional group that will become -Si(OH) ₃ in order to prevent film thickness variation and device malfunction. Substrates for flexible devices such as compounds with chemical structures. [Prior Art Document] [Patent Document]

[Patent Document 1] International Publication No. 2016/147958 [Patent Document 2] Japanese Patent Laid-Open No. 2016-225638

[Problem to be Solved by the Invention]

As mentioned above, it is necessary to replace the glass substrate used in the image display device with a polyimide film. When manufacturing an image display device, for example, in a TFT step, heat treatment is performed in a state where polyimide is laminated with an inorganic film, so outgassing gas generated from polyimide accumulates between polyimide and The interlayer of the inorganic film, so yellowing sometimes occurs. Therefore, it is desired that there is no change in color phase by heat treatment in the state where the inorganic film is laminated. However, it is difficult to balance heat resistance and yellowing prevention at the same time. Even if the heat resistance is improved by blending additives, it is still difficult to prevent yellowing. Also, in order to exhibit colorless and transparent polyimide itself, aliphatic diamines and fluorine-containing diamines are generally used to suppress the formation of charge transfer complexes between molecules or within molecules. However, aliphatic diamines are less rigid than aromatic diamines under severe conditions such as 350° C. or higher in the step of manufacturing TFTs in the manufacture of displays, so it is difficult to exhibit heat resistance. Fluorodiamine also has the problem of yellowing at high temperature. Therefore, a polyimide film having excellent heat resistance and little change in hue after heat treatment is particularly required. The present invention is made in view of such a situation, and an object of the present invention is to provide a polyimide resin composition and a polyimide film which are excellent in heat resistance and have little color change after heat treatment, and which can obtain excellent heat resistance and Polyimide precursor composition and varnish of polyimide film with less color change after heat treatment. [Means to solve the problem]

The inventors of the present invention have discovered a polyimide resin composition comprising a repeating unit of a polyimide derived from a specific fluorine-containing diamine and a tetracarboxylic acid having a specific alicyclic structure or aromatic ring and a specific silane compound The above-mentioned problems can be solved, and the invention has been completed.

式(1)中，X ¹為具有至少具有1個降莰烷骨架之脂環結構或芳香族環的4價基，X為選自於由單鍵、-NHCO-、-CONH-、-COO-及-OCO-構成之群組中之至少一者；式(2-1)及式(2-4)中，R ¹及R ²各自獨立地為氫、碳數1～6之烷基、苯基、或碳數1～6之胺基烷基；式(2-1)、式(2-2)、式(2-3)及式(2-4)中，R ³為碳數1～6之烷基。 [2]如前述[1]之聚醯亞胺樹脂組成物，其中，前述通式(1)表示之重複單元為下列通式(1-2)表示之重複單元； [化2]

式(1-2)中，X ¹為具有至少具有1個降莰烷骨架之脂環結構或芳香族環的4價基，X為選自於由單鍵、-NHCO-、-CONH-、-COO-及-OCO-構成之群組中之至少一者。 [3]如前述[1]或[2]之聚醯亞胺樹脂組成物，其中，前述式(1)中之X為單鍵。 [4]如前述[1]至[3]中任一項之聚醯亞胺樹脂組成物，其中，前述式(1)中之X ¹為選自於由下列式(3)、下列式(4)、下列式(5)、下列式(6)及下列式(7)構成之群組中之至少一者； [化3]

式(5)中，W為選自於由單鍵、碳數1～16之有機基構成之群組中之至少一者；式(6)中，Z為選自於由單鍵、碳數1～13之有機基構成之群組中之至少一者；式(7)中，R各自獨立地為甲基或三氟甲基，m為1或2，n為0～4之整數。 [5]如前述[1]至[4]中任一項之聚醯亞胺樹脂組成物，其中，前述式(1)中之X ¹為選自於由下列式(8)、下列式(9)及下列式(10)構成之群組中之至少一者； [化4]

。 [6]如前述[1]至[5]中任一項之聚醯亞胺樹脂組成物，其中，前述式(1)表示之重複單元，相對於前述聚醯亞胺的全部重複單元為10莫耳%以上。 [7]如前述[1]至[6]中任一項之聚醯亞胺樹脂組成物，其中，前述矽烷化合物的合計含量，相對於聚醯亞胺為10ppm以上且為50,000ppm以下。 [8]一種清漆，含有如前述[1]至[7]中任一項之聚醯亞胺樹脂組成物及有機溶劑。 [9]一種聚醯亞胺薄膜，係將如前述[8]之清漆塗佈在支持體上並進行加熱而獲得。 [10]如前述[9]之聚醯亞胺薄膜，其中，聚醯亞胺薄膜的玻璃轉移溫度為350℃以上。 [11]一種聚醯亞胺薄膜之製造方法，其特徵為：將如前述[8]之清漆塗佈在支持體上並進行加熱。 [12]一種聚醯亞胺前驅體組成物，含有： 具有下列通式(11)表示之重複單元的聚醯亞胺前驅體，及 選自於由下列通式(2-1)表示之化合物、下列通式(2-2)表示之化合物、下列通式(2-3)表示之化合物及下列通式(2-4)表示之化合物構成之群組中之至少一者之矽烷化合物； [化5]

式(11)中，X ²為具有至少具有1個降莰烷骨架之脂環結構或芳香族環的4價基，R ⁴及R ⁵各自獨立地為氫、碳數1～6之烷基、碳數3～9之烷基矽基，X為選自於由單鍵、-NHCO-、-CONH-、-COO-及-OCO-構成之群組中之至少一者；式(2-1)及式(2-4)中，R ¹及R ²各自獨立地為氫、碳數1～6之烷基、苯基、或碳數1～6之胺基烷基；式(2-1)、式(2-2)、式(2-3)及式(2-4)中，R ³為碳數1～6之烷基。 [13]如前述[12]之聚醯亞胺前驅體組成物，其中，前述矽烷化合物的合計含量，相對於聚醯亞胺前驅體為10ppm以上且為50,000ppm以下。 [14]一種清漆，含有如前述[12]或[13]之聚醯亞胺前驅體組成物及有機溶劑。 [15]一種聚醯亞胺薄膜，係將如前述[14]之清漆塗佈在支持體上並進行加熱而獲得。 [16]如前述[15]之聚醯亞胺薄膜，其中，聚醯亞胺薄膜的玻璃轉移溫度為350℃以上。 [17]一種聚醯亞胺薄膜之製造方法，其特徵為：將如前述[14]之清漆塗佈在支持體上並進行加熱。 [發明之效果] That is, the present invention relates to the following [1] to [17]. [1] A polyimide resin composition comprising: a polyimide having a repeating unit represented by the following general formula (1), and a compound selected from the following general formula (2-1), the following general formula A silane compound of at least one of the group consisting of the compound represented by the formula (2-2), the compound represented by the following general formula (2-3), and the compound represented by the following general formula (2-4);

In the formula (1), ^X1 is a tetravalent group having an alicyclic structure or an aromatic ring having at least one norbornane skeleton, and X is selected from single bonds, -NHCO-, -CONH-, -COO At least one of the group consisting of - and -OCO-; in formula (2-1) and formula (2-4), R ¹ and R ² are each independently hydrogen, an alkyl group with 1 to 6 carbons, Phenyl, or an aminoalkyl group with 1 to 6 carbons; in formula (2-1), formula (2-2), formula (2-3) and formula (2-4), R ³ is carbon number 1 ~6 alkyl groups. [2] The polyimide resin composition according to the aforementioned [1], wherein the repeating unit represented by the aforementioned general formula (1) is a repeating unit represented by the following general formula (1-2);

In the formula (1-2), X ^is a 4-valent group having an alicyclic structure or an aromatic ring having at least one norbornane skeleton, and X is selected from single bonds, -NHCO-, -CONH-, At least one of the group consisting of -COO- and -OCO-. [3] The polyimide resin composition according to the aforementioned [1] or [2], wherein X in the aforementioned formula (1) is a single bond. [4] The polyimide resin composition according to any one of the aforementioned [1] to [3], wherein ^X in the aforementioned formula (1) is selected from the following formula (3), the following formula ( 4), at least one of the group consisting of the following formula (5), the following formula (6) and the following formula (7); [Chem. 3]

In formula (5), W is at least one selected from the group consisting of a single bond and an organic group with 1 to 16 carbons; in formula (6), Z is selected from a group consisting of a single bond, carbon number At least one of the group consisting of 1-13 organic groups; in formula (7), R is each independently methyl or trifluoromethyl, m is 1 or 2, and n is an integer of 0-4. [5] The polyimide resin composition according to any one of the aforementioned [1] to [4], wherein ^X in the aforementioned formula (1) is selected from the following formula (8), the following formula ( 9) and at least one of the group formed by the following formula (10); [Chem. 4]

. [6] The polyimide resin composition according to any one of the aforementioned [1] to [5], wherein the repeating unit represented by the aforementioned formula (1) is 10 relative to all repeating units of the aforementioned polyimide. More than mole%. [7] The polyimide resin composition according to any one of [1] to [6] above, wherein the total content of the silane compounds is 10 ppm to 50,000 ppm based on the polyimide. [8] A varnish comprising the polyimide resin composition according to any one of the above-mentioned [1] to [7] and an organic solvent. [9] A polyimide film obtained by applying the varnish described in [8] above to a support and heating it. [10] The polyimide film according to the above [9], wherein the glass transition temperature of the polyimide film is 350° C. or higher. [11] A method for producing a polyimide film, characterized in that the varnish as described in [8] above is applied to a support and heated. [12] A polyimide precursor composition comprising: a polyimide precursor having a repeating unit represented by the following general formula (11), and a compound selected from compounds represented by the following general formula (2-1) , a silane compound of at least one of the group consisting of the compound represented by the following general formula (2-2), the compound represented by the following general formula (2-3), and the compound represented by the following general formula (2-4); [ Chemical 5]

In formula (11), ^X2 is a tetravalent group having an alicyclic structure or an aromatic ring having at least one norbornane skeleton, and ^R4 and ^R5 are each independently hydrogen, an alkyl group having 1 to 6 carbon atoms , an alkylsilyl group with 3 to 9 carbon atoms, X is at least one selected from the group consisting of a single bond, -NHCO-, -CONH-, -COO- and -OCO-; the formula (2- 1) and formula (2-4), R ¹ and R ² are each independently hydrogen, alkyl with 1 to 6 carbons, phenyl, or aminoalkyl with 1 to 6 carbons; formula (2- 1), in formula (2-2), formula (2-3) and formula (2-4), R ³ is an alkyl group having 1 to 6 carbon atoms. [13] The polyimide precursor composition according to [12] above, wherein the total content of the silane compounds is 10 ppm or more and 50,000 ppm or less with respect to the polyimide precursor. [14] A varnish comprising the polyimide precursor composition according to the aforementioned [12] or [13] and an organic solvent. [15] A polyimide film obtained by applying the varnish described in [14] above to a support and heating it. [16] The polyimide film according to [15] above, wherein the glass transition temperature of the polyimide film is 350° C. or higher. [17] A method for producing a polyimide film, characterized in that the varnish described in [14] above is coated on a support and heated. [Effect of Invention]

According to the present invention, it is possible to provide a polyimide resin composition and a polyimide film which are excellent in heat resistance and have little color change after heat treatment, and a polyimide film which is excellent in heat resistance and has little color change after heat treatment can be obtained. Polyimide precursor composition and varnish for amine film.

式(1)中，X ¹為具有至少具有1個降莰烷骨架之脂環結構或芳香族環的4價基，X為選自於由單鍵、-NHCO-、-CONH-、-COO-及-OCO-構成之群組中之至少一者。 式(2-1)及式(2-4)中，R ¹及R ²各自獨立地為氫、碳數1～6之烷基、苯基、或碳數1～6之胺基烷基。 式(2-1)、式(2-2)、式(2-3)及式(2-4)中，R ³為碳數1～6之烷基。 [Polyimide resin composition] The polyimide resin composition of the present invention contains: a polyimide having a repeating unit represented by the following general formula (1), and a polyimide selected from the following general formula (2-1) ), compounds represented by the following general formula (2-2), compounds represented by the following general formula (2-3), and compounds represented by the following general formula (2-4). [chemical 6]

In the formula (1), ^X1 is a tetravalent group having an alicyclic structure or an aromatic ring having at least one norbornane skeleton, and X is selected from single bonds, -NHCO-, -CONH-, -COO At least one of the group consisting of - and -OCO-. In formula (2-1) and formula (2-4), R ¹ and R ² are each independently hydrogen, alkyl having 1 to 6 carbons, phenyl, or aminoalkyl having 1 to 6 carbons. In formula (2-1), formula (2-2), formula (2-3) and formula (2-4), R ³ is an alkyl group having 1 to 6 carbon atoms.

The reason why a polyimide film having excellent heat resistance and little color change after heat treatment can be obtained by using the polyimide resin composition of the present invention is not clear, but is considered as follows. The polyimide resin composition of the present invention is considered to be particularly capable of suppressing side reactions at high temperatures because the silane compound is coordinated at the end of the polyimide, or the end of the polyimide reacts with the silane compound. Or decomposition and deterioration, etc., and the desorption of fluorine from the fluorine-containing diamine can be suppressed, which is considered to be able to obtain a polyimide film with excellent heat resistance and little change in hue after heat treatment.

式(1)中，X ¹為具有至少具有1個降莰烷骨架之脂環結構或芳香族環的4價基，X為選自於由單鍵、-NHCO-、-CONH-、-COO-及-OCO-構成之群組中之至少一者。 <Polyimide> The polyimide contained in the polyimide resin composition of the present invention has a repeating unit represented by the following general formula (1). [chemical 7]

In the formula (1), ^X1 is a tetravalent group having an alicyclic structure or an aromatic ring having at least one norbornane skeleton, and X is selected from single bonds, -NHCO-, -CONH-, -COO At least one of the group consisting of - and -OCO-.

式(1-1)中，X ¹為具有至少具有1個降莰烷骨架之脂環結構或芳香族環的4價基。 From the viewpoint of heat resistance, X in the aforementioned formula (1) is preferably a single bond. That is, the polyimide contained in the polyimide resin composition of the present invention preferably has a repeating unit represented by the following general formula (1-1). [chemical 8]

In formula (1-1), X ¹ is a tetravalent group having an alicyclic structure or an aromatic ring having at least one norbornane skeleton.

式(1-2)中，X ¹為具有至少具有1個降莰烷骨架之脂環結構或芳香族環的4價基，X為選自於由單鍵、-NHCO-、-CONH-、-COO-及-OCO-構成之群組中之至少一者。 The repeating unit represented by the aforementioned general formula (1) contained in the polyimide preferably includes a repeating unit represented by the following general formula (1-2), more preferably a repeating unit represented by the following general formula (1-2). [chemical 9]

In the formula (1-2), X ^is a 4-valent group having an alicyclic structure or an aromatic ring having at least one norbornane skeleton, and X is selected from single bonds, -NHCO-, -CONH-, At least one of the group consisting of -COO- and -OCO-.

式(1-2-1)～(1-2-5)中，X ¹為具有至少具有1個降莰烷骨架之脂環結構或芳香族環的4價基。 Examples of the repeating unit represented by the aforementioned formula (1-2) contained in polyimide include repeating units represented by the following formulas (1-2-1) to (1-2-5). From the viewpoint of heat resistance, It is preferably a repeating unit represented by formula (1-2-1). That is, in the aforementioned formula (1-2), X is at least one selected from the group consisting of a single bond, -NHCO-, -CONH-, -COO- and -OCO-, but considering heat resistance From the point of view, X is preferably a single bond. [chemical 10]

In the formulas (1-2-1) to (1-2-5), X ¹ is a tetravalent group having an alicyclic structure or an aromatic ring having at least one norbornane skeleton.

In the aforementioned formula (1), X ¹ is a tetravalent group having an alicyclic structure having at least one norbornane skeleton or an aromatic ring. X ¹ is preferably obtained by removing two dicarboxylic anhydride moieties (four carboxyl moieties) from tetracarboxylic dianhydride which is a raw material of constituent unit A derived from tetracarboxylic dianhydride described later. Similarly, in formula (1-1), formula (1-2), formula (1-2-1), formula (1-2-2), formula (1-2-3), formula (1-2 -4) and formula (1-2-5), X ¹ is a tetravalent group having an alicyclic structure having at least one norbornane skeleton or an aromatic ring. In addition, ^X1 is preferably obtained by removing two dicarboxylic anhydride moieties (four carboxyl moieties) from tetracarboxylic dianhydride which is a raw material of constituent unit A derived from tetracarboxylic dianhydride described later.

式(5)中，W為選自於由單鍵、碳數1～16之有機基構成之群組中之至少一者。 式(6)中，Z為選自於由單鍵、碳數1～13之有機基構成之群組中之至少一者。 式(7)中，R各自獨立地為甲基或三氟甲基，m為1或2，n為0～4之整數。 ^X in the aforementioned formula (1) is preferably selected from the group consisting of the following formula (3), the following formula (4), the following formula (5), the following formula (6) and the following formula (7) at least one. [chemical 11]

In formula (5), W is at least one member selected from the group consisting of a single bond and an organic group having 1 to 16 carbon atoms. In formula (6), Z is at least one member selected from the group consisting of a single bond and an organic group having 1 to 13 carbon atoms. In formula (7), R is each independently a methyl group or a trifluoromethyl group, m is 1 or 2, and n is an integer of 0-4.

The organic groups having 1 to 16 carbon atoms of W include alkenyl groups, phenylene groups, -NHCO-, -CONH-, -COO-, and -OCO-, each of which may have a substituent. The organic group having 1 to 13 carbon atoms of Z includes alkenyl, phenylene, -NHCO-, -CONH-, -COO-, and -OCO- each of which may have a substituent.

Among them, ^X1 in the aforementioned formula (1) is more preferably at least one selected from the group consisting of the following formula (8), the following formula (9) and the following formula (10). [chemical 12]

The glass transition temperature of the polyimide contained in the polyimide resin composition of the present invention is preferably 350°C or higher, more preferably 380°C or higher, and more preferably 400°C or higher. Since the glass transition temperature of polyimide is in the above-mentioned range, the polyimide film obtained by using the polyimide resin composition has excellent heat resistance and has little color change after heat treatment.

<Constituent units of polyimide> The above-mentioned polyimide contains the repeating unit represented by the above-mentioned general formula (1), but the structural units constituting the polyimide will be described. Polyimide has the structural unit A derived from tetracarboxylic dianhydride and the structural unit B derived from diamine.

(Constituent unit A) The constituent unit A is a constituent unit derived from a tetracarboxylic dianhydride, and is selected from a constituent unit (A1) derived from an alicyclic tetracarboxylic dianhydride having at least one norbornane skeleton and a constituent unit derived from an aromatic tetracarboxylic acid. At least one of the group consisting of the structural unit (A2) of dianhydride is preferably the structural unit (A1) from the viewpoint of reducing the change in hue, and is preferably the structural unit (A2) from the viewpoint of heat resistance. The structural unit (A1) derived from the alicyclic tetracarboxylic dianhydride which has at least one norbornane skeleton, and the structural unit (A2) derived from an aromatic tetracarboxylic dianhydride are more preferable.

Examples of the tetracarboxylic dianhydride providing the structural unit (A1) derived from tetracarboxylic dianhydride having at least one norbornane skeleton include compounds represented by the following formula (a1), compounds represented by the following formula (a2), A compound represented by the following formula (a3), etc. [chemical 13]

The compound represented by formula (a1) is norbornane-2-spiro-α-cyclopentanone-α'-spiro-2''-norbornane-5,5'',6,6''-tetracarboxylic acid Dianhydride (CpODA). The compound represented by formula (a2) is 5,5'-bis-2-norbornene-5,5',6,6'-tetracarboxylic acid-5,5',6,6'-dianhydride (BNBDA) . The compound represented by formula (a3) is decahydro-1H,3H-4,10:5,9-dimethyl-naphtho[2,3-c:6,7-c']difuran-1,3,6 ,8-tetraketone (DNDA).

Among them, the compound represented by formula (a1) is preferable, and the constituent unit A preferably contains a constituent unit derived from the compound represented by formula (a1). By using the structural unit derived from the compound represented by formula (a1) as the structural unit of polyimide, a polyimide film with little change in hue can be obtained.

Examples of the tetracarboxylic dianhydride providing the structural unit (A2) derived from the aromatic tetracarboxylic dianhydride include biphenyltetracarboxylic dianhydride (BPDA), 9,9-bis(3,4-dicarboxyphenyl ) phthalic anhydride (BPAF), pyromellitic dianhydride, 3,3',4,4'-(hexafluoroisopropylidene)diphthalic anhydride, 3,3',4,4'- Diphenylphenone tetracarboxylic dianhydride, 3,3',4,4'-diphenyl ketone tetracarboxylic dianhydride, 2,2',3,3'-diphenyl ketone tetracarboxylic dianhydride, etc. Among them, in consideration of heat resistance and reduction of hue change, it is preferably at least one selected from the group consisting of compounds represented by the following formula (a4) and compounds represented by the following formula (a5), More preferred are compounds represented by the following formula (a4). That is, the constituent unit A preferably includes at least one selected from the group consisting of a constituent unit derived from a compound represented by the following formula (a4) and a constituent unit derived from a compound represented by the following formula (a5), more preferably Contains a structural unit derived from a compound represented by the following formula (a4). [chemical 14]

The compound represented by the formula (a4) is biphenyltetracarboxylic dianhydride (BPDA), and its specific example includes 3,3',4,4'-biphenyltetracarboxylic dianhydride represented by the following formula (a4s) (s-BPDA), 2,3,3',4'-biphenyltetracarboxylic dianhydride (a-BPDA) represented by the following formula (a4a), 2,2',3, 3'-Biphenyltetracarboxylic dianhydride (i-BPDA). Among them, 3,3',4,4'-biphenyltetracarboxylic dianhydride (s-BPDA) represented by the following formula (a4s) is preferable. [chemical 15]

The compound represented by formula (a5) is 9,9'-bis(3,4-dicarboxyphenyl) stilbenic anhydride (BPAF). When the constituent unit A includes the constituent unit (A1) and the constituent unit (A2), the molar ratio [(A1)/(A2)] of the constituent unit (A1) to the constituent unit (A2) is preferably 50/50 to 90/ 10, preferably 50/50-80/20, more preferably 50/50-70/30.

When the constituent unit A includes constituent units derived from the compound represented by the aforementioned formula (a4), the silane compound contained in the polyimide resin composition of the present invention is preferably selected from the viewpoint of colorless transparency and heat resistance. The silane compound of at least one of the group consisting of the compound represented by the aforementioned general formula (2-1), the compound represented by the aforementioned general formula (2-3), and the compound represented by the aforementioned general formula (2-4), is more It is preferably at least one silane compound selected from the group consisting of the compound represented by the aforementioned general formula (2-3) and the compound represented by the aforementioned general formula (2-4), more preferably selected from the group consisting of the aforementioned At least one silane compound of the group consisting of compounds represented by the general formula (2-3).

Also, when the structural unit A includes a structural unit derived from the compound represented by the aforementioned formula (a5), the silane compound contained in the polyimide resin composition of the present invention is preferably selected from the viewpoint of colorless transparency and heat resistance. At least one silane compound selected from the group consisting of the compound represented by the aforementioned general formula (2-2), the compound represented by the aforementioned general formula (2-3), and the compound represented by the aforementioned general formula (2-4) , preferably selected from at least one silane compound selected from the group consisting of the compound represented by the aforementioned general formula (2-2) and the compound represented by the aforementioned general formula (2-3), more preferably selected from A silane compound of at least one of the group consisting of compounds represented by the aforementioned general formula (2-3).

The constitutional unit A may also contain constitutional units other than the aforementioned constitutional units. The tetracarboxylic dianhydride which provides such a structural unit is not specifically limited, The alicyclic tetracarboxylic dianhydride and the aliphatic tetracarboxylic dianhydride which provide structural units other than a structural unit (A1) are mentioned. Examples of the alicyclic tetracarboxylic dianhydride providing structural units other than the structural unit (A1) include 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 1,2,3,4-cyclohexane Butane tetracarboxylic dianhydride, dicyclohexyl tetracarboxylic dianhydride, etc. As an aliphatic tetracarboxylic dianhydride which provides the structural unit derived from an aliphatic tetracarboxylic dianhydride, 1,2,3,4- butane tetracarboxylic dianhydride etc. are mentioned. The structural unit arbitrarily contained in the structural unit A may be 1 type, and may be 2 or more types. In addition, in this specification, an aromatic tetracarboxylic dianhydride means a tetracarboxylic dianhydride containing one or more aromatic rings, and an alicyclic tetracarboxylic dianhydride means a tetracarboxylic dianhydride containing one or more alicyclic rings and does not contain an aromatic ring. Cyclic tetracarboxylic dianhydrides, aliphatic tetracarboxylic dianhydrides mean tetracarboxylic dianhydrides containing neither aromatic rings nor alicyclic rings.

式(b1)中，X為選自於由單鍵、-NHCO-、-CONH-、-COO-及-OCO-構成之群組中之至少一者。 (Structural Unit B) The structural unit B is a structural unit derived from a diamine, and includes a structural unit (B1) derived from a compound represented by formula (b1). When the structural unit (B1) is contained in the structural unit B, heat resistance is excellent, and especially when combined with a silane compound, the effect of reducing yellowness is excellent. [chemical 16]

In formula (b1), X is at least one member selected from the group consisting of a single bond, -NHCO-, -CONH-, -COO-, and -OCO-.

The structural unit (B1) preferably contains a structural unit (B11) derived from a compound represented by the following formula (b11). [chemical 17]

式(b12)中，X為選自於由單鍵、-NHCO-、-CONH-、-COO-及-OCO-構成之群組中之至少一者。 Moreover, the structural unit (B1) preferably contains a structural unit (B12) derived from a compound represented by the following formula (b12). [chemical 18]

In formula (b12), X is at least one member selected from the group consisting of a single bond, -NHCO-, -CONH-, -COO-, and -OCO-.

The constituent unit (B12) comprises a constituent unit (B121) derived from a compound represented by the following formula (b121), a constituent unit (B122) derived from a compound represented by the following formula (b122), and a constituent unit represented by the following formula (b123) At least one of the group consisting of the structural unit (B123) of the compound, in consideration of heat resistance, preferably includes a structural unit (B121) derived from a compound represented by the following formula (b121), more preferably derived from the following formula ( The structural unit (B121) of the compound represented by b121). [chemical 19]

The compound represented by the formula (b121) is 2,2'-bis(trifluoromethyl)benzidine (TFMB). By including the structural unit (B1) in the structural unit B, a polyimide film having excellent heat resistance and little change in hue after heat treatment can be obtained.

The structural unit B may also contain structural units other than the structural unit (B1). Diamines providing such structural units are not particularly limited, and examples include: 3,5-diaminobenzoic acid (3,5-DABA), 9,9-bis(4-aminophenyl) fluorine (BAFL) , 4-aminobenzoic acid-4-aminophenyl ester (4-BAAB), 1,4-phenylenediamine, p-xylylenediamine, 1,5-diaminonaphthalene, 2,2'-dimethyl Biphenyl-4,4'-diamine, 4,4'-diaminodiphenylmethane, 1,4-bis[2-(4-aminophenyl)-2-propyl]benzene, 2 ,2-bis(4-aminophenyl)hexafluoropropane, 4,4'-diaminobenzanilide, 1-(4-aminophenyl)-2,3-dihydro-1,3 ,3-Trimethyl-1H-inden-5-amine, α,α'-bis(4-aminophenyl)-1,4-diisopropylbenzene, N,N'-bis(4-amine phenyl) terephthalamide, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, and 1,4-bis(4-aminophenoxy)benzene, etc. Aromatic diamines other than compounds represented by formula (b1); alicyclic diamines such as 1,3-bis(aminomethyl)cyclohexane and 1,4-bis(aminomethyl)cyclohexane and aliphatic diamines such as ethylenediamine and hexamethylenediamine.

式(b2)表示之化合物為9,9-雙(4-胺基苯基)茀(BAFL)。 當構成單元B包含構成單元(B2)時，構成單元(B1)與構成單元(B2)之莫耳比[(B1)/(B2)]宜為50/50～90/10，較佳為50/50～80/20，更佳為50/50～70/30。 Among the structural units other than the structural unit (B1), it is preferable to contain a structural unit (B2) derived from a compound represented by the following formula (b2). [chemical 20]

The compound represented by the formula (b2) is 9,9-bis(4-aminophenyl)fluorene (BAFL). When the constituent unit B includes the constituent unit (B2), the molar ratio [(B1)/(B2)] of the constituent unit (B1) to the constituent unit (B2) is preferably 50/50 to 90/10, preferably 50 /50～80/20, more preferably 50/50～70/30.

When the constituent unit B includes the constituent unit (B1) and the constituent unit (B2), considering colorless transparency and heat resistance, the silane compound contained in the polyimide resin composition of the present invention is preferably selected from A silane compound of at least one of the compound represented by the aforementioned general formula (2-2), the compound represented by the aforementioned general formula (2-3), and the compound represented by the aforementioned general formula (2-4), preferably It is at least one silane compound selected from the group consisting of the compound represented by the aforementioned general formula (2-2) and the compound represented by the aforementioned general formula (2-3), more preferably selected from the group consisting of the aforementioned general formula At least one silane compound of the group consisting of compounds represented by formula (2-3).

In addition, in this specification, an aromatic diamine means a diamine containing one or more aromatic rings, an alicyclic diamine means a diamine containing one or more alicyclic rings and no aromatic ring, and an aliphatic diamine Means a diamine containing neither an aromatic ring nor an aliphatic ring. The structural unit arbitrarily contained in the structural unit B may be 1 type, and may be 2 or more types.

(Manufacturing method of polyimide) The polyimide contained in the polyimide resin composition of the present invention can be obtained by making the tetracarboxylic acid component providing the structural unit A described in the item of the above-mentioned <Each structural unit of the polyimide> and providing The diamine component constituting the unit B is reacted and produced.

As far as the specific reaction method is concerned, it can be enumerated: (1) Add the tetracarboxylic acid component, the diamine component, and the reaction solvent into the reactor, stir at 10-110° C. for 0.5-30 hours, then raise the temperature and carry out The method of amination reaction; (2) After adding the diamine component and the reaction solvent into the reactor and dissolving it, adding the tetracarboxylic acid component, stirring at 10-110°C for 0.5-30 hours if necessary, then heating up and carrying out (3) adding tetracarboxylic acid component, diamine component, and reaction solvent into the reactor, immediately raising the temperature and performing imidization reaction, etc.

In the imidization reaction, it is preferable to use a Dean-Stark (Dean-Stark) apparatus or the like, and to carry out the reaction while removing water generated during production. By performing such an operation, the degree of polymerization and the imidization rate can be further increased.

In the above imidization reaction, known imidization catalysts can be used. As an imidization catalyst, an alkali catalyst or an acid catalyst is mentioned. Alkaline catalysts include: pyridine, quinoline, isoquinoline, α-picoline, β-picoline, 2,4-lutidine, 2,6-lutidine, trimethylamine, triethyl Amine, tripropylamine, tributylamine, triethylenediamine, imidazole, N,N-dimethylaniline, N,N-diethylaniline and other organic base catalysts; potassium hydroxide, sodium hydroxide, potassium carbonate , sodium carbonate, potassium bicarbonate, sodium bicarbonate and other inorganic alkali catalysts. Moreover, examples of the acid catalyst include: crotonic acid, acrylic acid, trans-3-hexenoic acid, cinnamic acid, benzoic acid, methylbenzoic acid, hydroxybenzoic acid, terephthalic acid, benzenesulfonic acid, p-toluenesulfonic acid , naphthalenesulfonic acid, etc. These imidization catalysts can be used individually or in combination of 2 or more types. Among the above, from the viewpoint of operability, it is preferable to be an alkali catalyst, preferably an organic alkali catalyst, more preferably at least one selected from triethylamine and triethylenediamine, and more preferably triethylamine. amine.

From the viewpoint of reaction rate and gelation suppression, the temperature of imidization reaction is preferably 120-250°C, more preferably 160-200°C. Also, the reaction time is preferably 0.5 to 10 hours from the start of distilling off the produced water.

By the above method, a polyimide solution dissolved in a solvent can be obtained. The concentration of polyimide in the obtained solution is preferably 1-50% by mass, preferably 3-35% by mass, more preferably 5-30% by mass. Next, raw materials and the like used in this production method will be described.

[tetracarboxylic acid component] The tetracarboxylic acid component used as a raw material in this production method contains an alicyclic tetracarboxylic dianhydride having at least one norbornane skeleton as a compound providing a structural unit (A1), and an alicyclic tetracarboxylic dianhydride as a compound providing a structural unit (A2 ) compounds of aromatic tetracarboxylic dianhydrides. Among them, as the compound providing the constituent unit (A1), preferably, a compound represented by the formula (a1), a compound represented by the formula (a2), a compound represented by the formula (a3), etc. are preferably mentioned, and the compound represented by the formula (a1) is more preferable. good. Moreover, as a compound which provides a structural unit (A2), Preferably, the compound represented by a formula (a4) and the compound represented by a formula (a5) are mentioned, More preferably, it is a compound represented by a formula (a4). When the compound providing the structural unit (A1) and the compound providing the structural unit (A2) are contained, the molar ratio of the compound providing the structural unit (A1) to the compound providing the structural unit (A2) [(A1)/(A2) ] preferably 50/50-90/10, preferably 50/50-80/20, more preferably 50/50-70/30. Other tetracarboxylic dianhydrides may also be contained in the tetracarboxylic acid component, and other tetracarboxylic dianhydrides are not particularly limited, and examples thereof include alicyclic tetracarboxylic dianhydrides, aliphatic tetracarboxylic dianhydrides, and compounds other than those providing constituent units (A1). Carboxylic dianhydride. The tetracarboxylic acid component is not limited to tetracarboxylic dianhydride, and derivatives thereof may be used. As this derivative, tetracarboxylic acid and the alkyl ester of this tetracarboxylic acid are mentioned. Among these, tetracarboxylic dianhydride is preferable.

[Diamine component] The diamine component used as a raw material in this manufacturing method contains the compound represented by the formula (b1) as a compound which provides a structural unit (B1). Among the compounds represented by the formula (b1), the compound represented by the formula (b11) is preferable, the compound represented by the formula (b12) is preferable, and the compound represented by the formula (b121) is more preferable. Other diamines may be contained in the diamine component, and other diamines are not particularly limited, and examples thereof include aromatic diamines, alicyclic diamines, and aliphatic diamines other than the compound represented by formula (b1). Among them, the compound represented by the formula (b2) is preferable. When containing the compound represented by formula (b2), the molar ratio [(b1)/(b2)] of the compound represented by formula (b1) to the compound represented by formula (b2) should be 50/50～90/10, relatively Preferably it is 50/50-80/20, more preferably 50/50-70/30. The diamine component is not limited to diamine, and derivatives thereof may be used. As this derivative, the diisocyanate corresponding to diamine is mentioned. Among these, diamine is preferable.

In the aforementioned reaction, the diamine component is preferably 0.9 to 1.1 mol with respect to the tetracarboxylic acid component.

[blocking agent] Moreover, when producing polyimide, it is also possible to use an end-blocking agent in addition to the above-mentioned tetracarboxylic acid component and diamine component. The blocking agent is preferably monoamine or dicarboxylic acid. The amount of the capping agent to be introduced is preferably 0.0001-0.1 mole, more preferably 0.001-0.06 mole relative to 1 mole of the tetracarboxylic acid component. Examples of monoamine blocking agents include: methylamine, ethylamine, propylamine, butylamine, benzylamine, 4-methylbenzylamine, 4-ethylbenzylamine, 4-dodecylbenzylamine, 3-methylbenzylamine, Benzylbenzylamine, 3-ethylbenzylamine, aniline, 3-methylaniline, 4-methylaniline, etc. Among these, benzylamine and aniline are preferable. The dicarboxylic acid-type end-capping agent is preferably a dicarboxylic acid, and a part of the ring can also be closed. For example, phthalic acid, phthalic anhydride, 4-chlorophthalic acid, tetrafluorophthalic acid, 2,3-diphenyl ketone dicarboxylic acid, 3,4-diphenyl ketone Dicarboxylic acid, cyclopentane-1,2-dicarboxylic acid, 4-cyclohexene-1,2-dicarboxylic acid, etc. Among these, phthalic acid and phthalic anhydride are more preferable.

[solvent] The solvent used in the production of the aforementioned polyimide may be any solvent as long as it can dissolve the produced polyimide. For example, an aprotic solvent, a phenol type solvent, an ether type solvent, a carbonate type solvent, etc. are mentioned.

Specific examples of aprotic solvents include: N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam Amide-based solvents such as amine, 1,3-dimethylimidazolidinone, and tetramethylurea; lactone-based solvents such as γ-butyrolactone and γ-valerolactone; hexamethylphosphoramide, hexamethyl Phosphate-containing amide-based solvents such as phosphine triamide; sulfur-containing solvents such as dimethylsulfide, dimethylsulfoxide, and cyclobutylene; ketone-based solvents such as acetone, methyl ethyl ketone, cyclohexanone, and methylcyclohexanone ; Ester solvents such as acetic acid (2-methoxy-1-methylethyl ester), etc.

Specific examples of phenolic solvents 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. Specific examples of ether solvents include: 1,2-dimethoxyethane, bis(2-methoxyethyl)ether, 1,2-bis(2-methoxyethoxy)ethane, Bis[2-(2-methoxyethoxy)ethyl]ether, tetrahydrofuran, 1,4-dioxane, etc. Specific examples of carbonate-based solvents include diethyl carbonate, ethylmethyl carbonate, ethylene carbonate, and propylene carbonate. Among the above-mentioned reaction solvents, amide-based solvents or lactone-based solvents are preferred, amide-based solvents are preferred, and N-methyl-2-pyrrolidone is more preferred. The above reaction solvents may be used alone or in combination of two or more.

式(2-1)及式(2-4)中，R ¹及R ²各自獨立地為氫、碳數1～6之烷基、苯基、或碳數1～6之胺基烷基。式(2-1)、式(2-2)、式(2-3)及式(2-4)中，R ³為碳數1～6之烷基。 藉由含有該矽烷化合物，可獲得具耐熱性且低黃色度的薄膜。 考量無色透明性及耐熱性的觀點，本發明之聚醯亞胺樹脂組成物中含有的矽烷化合物宜為選自於由前述通式(2-2)表示之化合物、前述通式(2-3)表示之化合物及前述通式(2-4)表示之化合物構成之群組中之至少一者之矽烷化合物，較佳為選自於由前述通式(2-2)表示之化合物及前述通式(2-3)表示之化合物構成之群組中之至少一者之矽烷化合物，更佳為選自於由前述通式(2-3)表示之化合物構成之群組中之至少一者之矽烷化合物。 <Silane compound> The silane compound contained in the polyimide resin composition of the present invention is selected from the compound represented by the following general formula (2-1), the compound represented by the following general formula (2-2), the following A silane compound of at least one of the group consisting of the compound represented by the general formula (2-3) and the compound represented by the following general formula (2-4). [chem 21]

In formula (2-1) and formula (2-4), R ¹ and R ² are each independently hydrogen, alkyl having 1 to 6 carbons, phenyl, or aminoalkyl having 1 to 6 carbons. In formula (2-1), formula (2-2), formula (2-3) and formula (2-4), R ³ is an alkyl group having 1 to 6 carbon atoms. By containing this silane compound, a thin film with heat resistance and low yellowness can be obtained. From the viewpoint of colorless transparency and heat resistance, the silane compound contained in the polyimide resin composition of the present invention is preferably selected from the compounds represented by the aforementioned general formula (2-2), the aforementioned general formula (2-3 ) represented by the compound represented by the aforementioned general formula (2-4) and at least one silane compound in the group consisting of the compound represented by the aforementioned general formula (2-4), preferably selected from the compounds represented by the aforementioned general formula (2-2) and the aforementioned At least one silane compound selected from the group consisting of compounds represented by formula (2-3), more preferably at least one selected from the group consisting of compounds represented by the aforementioned general formula (2-3) Silane compounds.

In formula (2-1), R ¹ and R ² are each independently hydrogen, alkyl having 1 to 6 carbons, phenyl, or aminoalkyl having 1 to 6 carbons, preferably selected from the group consisting of hydrogen and at least one of the group consisting of phenyl, more preferably hydrogen. In formula (2-1), R ³ is an alkyl group having 1 to 6 carbon atoms, preferably at least one selected from the group consisting of methyl and ethyl, more preferably ethyl. In formula (2-2), R ³ is an alkyl group having 1 to 6 carbon atoms, preferably at least one selected from the group consisting of methyl and ethyl, more preferably ethyl. In formula (2-3), R ³ is an alkyl group having 1 to 6 carbon atoms, preferably at least one selected from the group consisting of methyl and ethyl, more preferably methyl. In the formula (2-4), R ¹ and R ² are each independently hydrogen, an alkyl group having 1 to 6 carbons, a phenyl group, or an aminoalkyl group having 1 to 6 carbons, preferably 1 to 6 carbons The alkyl group. In formula (2-4), R ³ is an alkyl group having 1 to 6 carbon atoms, preferably at least one selected from the group consisting of methyl and ethyl, more preferably ethyl.

The aforementioned silane compounds can be commercially available. As a preferred commercially available silane compound, Shin-Etsu Chemical Co., Ltd. KBE9007N (3-isocyanate propyl triethoxysilane, formula (2-2) The compound when R ³ is ethyl), KBM9659 (refer to - (trimethoxysilylpropyl) isocyanurate, the compound when R ³ is methyl in formula (2-3), KBM573 (N -Phenyl-3-aminopropyltrimethoxysilane, compound when R ³ is methyl in formula (2-1), KBE9103P (3-triethoxysilyl-N-(1,3- Dimethyl-butylene) propylamine, the compound when ^R3 is ethyl in formula (2-4), KBE903 (3-aminopropyltriethoxysilane, ^R3 in formula (2-1) is Compound when ethyl), KBM903 (3-aminopropyltrimethoxysilane, compound when R ³ is methyl in formula (2-1)), etc.

The content of the aforementioned silane compound is preferably not less than 10 ppm and not more than 50,000 ppm, preferably not less than 1,000 ppm and not more than 20,000 ppm, more preferably not less than 2,000 ppm and not more than 15,000 ppm, more preferably not less than 3,000 ppm and not more than 12,000 ppm relative to the polyimide , and more preferably not less than 3,000ppm and not more than 8,000ppm. When the amount of the silane compound falls within this range, a thin film having heat resistance and little change in hue after heat treatment can be obtained. In addition, in this specification, "ppm" means mass parts per million.

The glass transition temperature of the polyimide resin composition of the present invention is preferably above 350°C, preferably above 380°C, more preferably above 400°C. When the glass transition temperature of the polyimide resin composition is within the above range, a polyimide film having excellent heat resistance and little change in hue after heat treatment can be obtained.

[varnish] The varnish of the present invention contains the aforementioned polyimide resin composition and an organic solvent. That is, the polyimide, the silane compound, and an organic solvent are contained, and the polyimide and the silane compound are dissolved in the organic solvent. The organic solvent is not particularly limited as long as it can dissolve the polyimide and the silane compound, and it is preferable to use the above-mentioned compounds as solvents used in the production of polyimide alone or in combination of two or more. The varnish of the present invention may be obtained by directly dissolving a silane compound in the above-mentioned polyimide solution, or may be obtained by further mixing and dissolving the polyimide solution with a dilution solvent and a silane compound.

The polyimide contained in the varnish of the present invention has solvent solubility, so it can be made into a stable high-concentration varnish at room temperature. The varnish of the present invention preferably contains 3-40% by mass of polyimide, more preferably 5-30% by mass. The viscosity of the varnish should be 0.1-100Pa･s, more preferably 0.1-20Pa･s. The viscosity of the varnish is the value measured at 25°C with an E-type viscometer. In addition, the varnish of the present invention may also contain inorganic fillers, adhesion promoters, release agents, flame retardants, ultraviolet stabilizers, surfactants, leveling agents, Agents, defoamers, fluorescent whitening agents, crosslinking agents, polymerization initiators, photosensitizers and other additives. The manufacturing method of the varnish of this invention is not specifically limited, A well-known method can be used. For example, it can be obtained by mixing and dissolving the above-mentioned silane compound in a solution of polyimide obtained by the above-mentioned production method, and further mixing a solvent and adjusting the concentration as necessary.

[Polyimide film and method for producing polyimide film] The polyimide film of the present invention is preferably manufactured using the aforementioned varnish.

The method of producing the polyimide film using the varnish of the present invention is not particularly limited, and known methods can be used. For example, a polyimide film can be produced by coating or forming the varnish of the present invention into a film on a smooth support such as a glass plate, metal plate, or plastic, and removing the solvent. That is to say, the polyimide film of the present invention is preferably a polyimide film obtained by coating the aforementioned varnish on a support and heating it, and the manufacturing method of the polyimide film of the present invention is preferably to apply the aforementioned varnish A method of coating on a support and heating.

The thickness of the polyimide film of the present invention can be appropriately selected depending on the application and the like, and is preferably at least 1 μm, preferably at least 5 μm, and more preferably at least 7 μm. Moreover, it is preferably 250 μm or less, preferably 100 μm or less, more preferably 50 μm or less, and still more preferably 20 μm or less. When the thickness is in the above-mentioned range, practical use can be achieved. The thickness of the polyimide film can be easily controlled by adjusting the solid content concentration and viscosity of the varnish.

The glass transition temperature of the polyimide film of the present invention is preferably above 350°C, preferably above 380°C, more preferably above 400°C. When the glass transition temperature of the polyimide film is in the above-mentioned range, it has excellent heat resistance and little change in hue after heat treatment.

The polyimide film of the present invention can be ideally used as a film for various members such as color filters, flexible displays, semiconductor parts, and optical members. The polyimide film of the present invention can be ideally used as a substrate of image display devices such as liquid crystal displays and OLED displays.

式(11)中，X ²為具有至少具有1個降莰烷骨架之脂環結構或芳香族環的4價基，R ⁴及R ⁵各自獨立地為氫、碳數1～6之烷基、碳數3～9之烷基矽基，X為選自於由單鍵、-NHCO-、-CONH-、-COO-及-OCO-構成之群組中之至少一者。 式(2-1)及式(2-4)中，R ¹及R ²各自獨立地為氫、碳數1～6之烷基、苯基、或碳數1～6之胺基烷基。 式(2-1)、式(2-2)、式(2-3)及式(2-4)中，R ³為碳數1～6之烷基。 [Polyimide precursor composition] The polyimide precursor composition of the present invention contains: a polyimide precursor having a repeating unit represented by the following general formula (11), and a polyimide precursor selected from the following general formula Among the compounds represented by (2-1), the compounds represented by the following general formula (2-2), the compounds represented by the following general formula (2-3), and the compounds represented by the following general formula (2-4) at least one silane compound. [chem 22]

In formula (11), ^X2 is a tetravalent group having an alicyclic structure or an aromatic ring having at least one norbornane skeleton, and ^R4 and ^R5 are each independently hydrogen, an alkyl group having 1 to 6 carbon atoms . An alkylsilyl group having 3 to 9 carbon atoms, X is at least one member selected from the group consisting of a single bond, -NHCO-, -CONH-, -COO-, and -OCO-. In formula (2-1) and formula (2-4), R ¹ and R ² are each independently hydrogen, alkyl having 1 to 6 carbons, phenyl, or aminoalkyl having 1 to 6 carbons. In formula (2-1), formula (2-2), formula (2-3) and formula (2-4), R ³ is an alkyl group having 1 to 6 carbon atoms.

In addition to using the polyimide resin composition to obtain the polyimide film as described above, by imidizing the polyimide precursor composition of the present invention, it is also possible to obtain excellent heat resistance and heat treatment A polyimide film with little color change afterwards.

式(11)中，X ²為具有至少具有1個降莰烷骨架之脂環結構或芳香族環的4價基，R ⁴及R ⁵各自獨立地為氫、碳數1～6之烷基、碳數3～9之烷基矽基，X為選自於由單鍵、-NHCO-、-CONH-、-COO-及-OCO-構成之群組中之至少一者。 <Polyimide Precursor> The polyimide precursor contained in the polyimide precursor composition of the present invention has a repeating unit represented by the following general formula (11). [chem 23]

In formula (11), ^X2 is a tetravalent group having an alicyclic structure or an aromatic ring having at least one norbornane skeleton, and ^R4 and ^R5 are each independently hydrogen, an alkyl group having 1 to 6 carbon atoms . An alkylsilyl group having 3 to 9 carbon atoms, X is at least one member selected from the group consisting of a single bond, -NHCO-, -CONH-, -COO-, and -OCO-.

式(11)中，X ²為具有至少具有1個降莰烷骨架之脂環結構或芳香族環的4價基，R ⁴及R ⁵各自獨立地為氫、碳數1～6之烷基、碳數3～9之烷基矽基。 From the viewpoint of heat resistance, X in the aforementioned formula (11) is preferably a single bond. That is, the polyimide precursor contained in the polyimide precursor composition of the present invention preferably has a repeating unit represented by the following general formula (11-1). [chem 24]

In formula (11), ^X2 is a tetravalent group having an alicyclic structure or an aromatic ring having at least one norbornane skeleton, and ^R4 and ^R5 are each independently hydrogen, an alkyl group having 1 to 6 carbon atoms , Alkyl silicon group with 3-9 carbon atoms.

式(11-2)中，X ²為具有至少具有1個降莰烷骨架之脂環結構或芳香族環的4價基，R ⁴及R ⁵各自獨立地為氫、碳數1～6之烷基、碳數3～9之烷基矽基，X為選自於由單鍵、-NHCO-、-CONH-、-COO-及-OCO-構成之群組中之至少一者。 The repeating unit represented by the aforementioned general formula (11) contained in the polyimide precursor preferably includes a repeating unit represented by the following general formula (11-2), more preferably a repeating unit represented by the following general formula (11-2). [chem 25]

In the formula (11-2), X ² is a tetravalent group having an alicyclic structure or an aromatic ring having at least one norbornane skeleton, R ⁴ and R ⁵ are each independently hydrogen, carbon number 1 to 6 An alkyl group, an alkylsilyl group having 3 to 9 carbon atoms, and X is at least one member selected from the group consisting of a single bond, -NHCO-, -CONH-, -COO-, and -OCO-.

式(11-2-1)～(11-2-5)中，X ²為具有至少具有1個降莰烷骨架之脂環結構或芳香族環的4價基，R ⁴及R ⁵各自獨立地為氫、碳數1～6之烷基、碳數3～9之烷基矽基。 As the repeating unit represented by the aforementioned formula (11-2) contained in the polyimide precursor, repeating units represented by the following formulas (11-2-1) to (11-2-5) can be cited, and heat resistance is considered From a viewpoint, it is preferably a repeating unit represented by formula (11-2-1). That is, in the aforementioned formula (11-2), X is at least one selected from the group consisting of a single bond, -NHCO-, -CONH-, -COO-, and -OCO-, in consideration of heat resistance Viewpoint, X is preferably a single bond. [chem 26]

In the formulas (11-2-1) to (11-2-5), X ² is a tetravalent group having an alicyclic structure or an aromatic ring having at least one norbornane skeleton, and R ⁴ and R ⁵ are independently Ground is hydrogen, an alkyl group having 1 to 6 carbons, and an alkylsilyl group having 3 to 9 carbons.

In the aforementioned formula (11), X ² is a tetravalent group having an alicyclic structure having at least one norbornane skeleton or an aromatic ring. X ² is preferably obtained by removing two dicarboxylic anhydride moieties (four carboxyl moieties) from tetracarboxylic dianhydride which is a raw material of constituent unit AA derived from tetracarboxylic dianhydride described later. Similarly, formula (11-1), formula (11-2), formula (11-2-1), formula (11-2-2), formula (11-2-3), formula (11-2- 4) and formula (11-2-5), X ² is a tetravalent group having an alicyclic structure having at least one norbornane skeleton or an aromatic ring. In addition, ^X2 is preferably obtained by removing two dicarboxylic anhydride moieties (four carboxyl moieties) from tetracarboxylic dianhydride which is a raw material of constituent unit AA derived from tetracarboxylic dianhydride described later.

式(5)中，W為選自於由單鍵、碳數1～16之有機基構成之群組中之至少一者。 式(6)中，Z為選自於由單鍵、碳數1～13之有機基構成之群組中之至少一者。 式(7)中，R各自獨立地為甲基或三氟甲基，m為1或2，n為0～4之整數。 ^X in the aforementioned formula (11) is preferably selected from the group consisting of the following formula (3), the following formula (4), the following formula (5), the following formula (6) and the following formula (7) at least one. [chem 27]

In formula (5), W is at least one member selected from the group consisting of a single bond and an organic group having 1 to 16 carbon atoms. In formula (6), Z is at least one member selected from the group consisting of a single bond and an organic group having 1 to 13 carbon atoms. In formula (7), R is each independently a methyl group or a trifluoromethyl group, m is 1 or 2, and n is an integer of 0-4.

The organic groups having 1 to 16 carbon atoms of W include alkenyl groups, phenylene groups, -NHCO-, -CONH-, -COO-, and -OCO-, each of which may have a substituent. The organic group having 1 to 13 carbon atoms of Z includes alkenyl, phenylene, -NHCO-, -CONH-, -COO-, and -OCO- each of which may have a substituent.

Among them, X ² in the aforementioned formula (11) is more preferably at least one selected from the group consisting of the following formula (8), the following formula (9) and the following formula (10). [chem 28]

In the aforementioned formula (11), R ⁴ and R ⁵ are each independently hydrogen, an alkyl group having 1 to 6 carbons, or an alkylsilyl group having 3 to 9 carbons, preferably hydrogen.

<Constituent units of polyimide precursor> The aforementioned polyimide precursor contains the repeating unit represented by the aforementioned general formula (11), but the structural units constituting the polyimide precursor will be described. The polyimide precursor has a constituent unit AA derived from tetracarboxylic dianhydride and a constituent unit BA derived from diamine, but each constituent unit is the same as that described above in <Each constituent unit of polyimide> . That is, the constituent unit AA derived from tetracarboxylic dianhydride is the same as the constituent unit A derived from tetracarboxylic dianhydride, and the preferred constituent units are also the same, and the constituent unit BA derived from diamine and the constituent unit B derived from diamine are The same, preferred constituent units are also the same. It will be described in detail below.

(Constituent unit AA) The constituent unit AA is a constituent unit derived from a tetracarboxylic dianhydride, and is selected from a constituent unit (AA1) derived from an alicyclic tetracarboxylic dianhydride having at least one norbornane skeleton and a constituent unit derived from an aromatic tetracarboxylic acid At least one of the group consisting of the constituent unit (AA2) of the dianhydride is preferably the constituent unit (AA1) from the viewpoint of reducing the hue change, and preferably the constituent unit (AA2) from the viewpoint of heat resistance. It is more preferable that it is the structural unit (AA1) derived from the alicyclic tetracarboxylic dianhydride which has at least one norbornane skeleton, and the structural unit (AA2) derived from an aromatic tetracarboxylic dianhydride.

Examples of the tetracarboxylic dianhydride providing the structural unit (AA1) derived from tetracarboxylic dianhydride having at least one norbornane skeleton include compounds represented by the following formula (a1), compounds represented by the following formula (a2), A compound represented by the following formula (a3), etc. [chem 29]

The compound represented by formula (a1) is norbornane-2-spiro-α-cyclopentanone-α'-spiro-2''-norbornane-5,5'',6,6''-tetracarboxylic acid Dianhydride (CpODA). The compound represented by formula (a2) is 5,5'-bis-2-norbornene-5,5',6,6'-tetracarboxylic acid-5,5',6,6'-dianhydride (BNBDA) . The compound represented by formula (a3) is decahydro-1H,3H-4,10:5,9-dimethyl-naphtho[2,3-c:6,7-c']difuran-1,3,6 ,8-tetraketone (DNDA).

Among them, the compound represented by formula (a1) is preferable, and the constituent unit AA preferably contains a constituent unit derived from the compound represented by formula (a1). By using the structural unit derived from the compound represented by formula (a1) as the structural unit of the polyimide precursor, a polyimide film with little change in hue can be obtained.

Examples of tetracarboxylic dianhydrides that provide constituent units (AA2) derived from aromatic tetracarboxylic dianhydrides include biphenyltetracarboxylic dianhydride (BPDA), 9,9-bis(3,4-dicarboxyphenyl ) phthalic anhydride (BPAF), pyromellitic dianhydride, 3,3',4,4'-(hexafluoroisopropylidene)diphthalic anhydride, 3,3',4,4'- Diphenylphenone tetracarboxylic dianhydride, 3,3',4,4'-diphenyl ketone tetracarboxylic dianhydride, 2,2',3,3'-diphenyl ketone tetracarboxylic dianhydride, etc. Among them, in consideration of heat resistance and reduction of hue change, it is preferably at least one selected from the group consisting of compounds represented by the following formula (a4) and compounds represented by the following formula (a5), More preferred are compounds represented by the following formula (a4). That is, the constituent unit AA preferably includes at least one selected from the group consisting of a constituent unit derived from a compound represented by the following formula (a4) and a constituent unit derived from a compound represented by the following formula (a5), more preferably Contains a structural unit derived from a compound represented by the following formula (a4). [chem 30]

The compound represented by the formula (a4) is biphenyltetracarboxylic dianhydride (BPDA), and its specific example includes 3,3',4,4'-biphenyltetracarboxylic dianhydride represented by the following formula (a4s) (s-BPDA), 2,3,3',4'-biphenyltetracarboxylic dianhydride (a-BPDA) represented by the following formula (a4a), 2,2',3, 3'-Biphenyltetracarboxylic dianhydride (i-BPDA). Among them, 3,3',4,4'-biphenyltetracarboxylic dianhydride (s-BPDA) represented by the following formula (a4s) is preferable. [chem 31]

The compound represented by formula (a5) is 9,9'-bis(3,4-dicarboxyphenyl) stilbenic anhydride (BPAF). When the constituent unit AA includes the constituent unit (AA1) and the constituent unit (AA2), the molar ratio [(AA1)/(AA2)] of the constituent unit (AA1) to the constituent unit (AA2) is preferably 50/50 to 90/ 10, preferably 50/50-80/20, more preferably 50/50-70/30.

When the structural unit AA contains a structural unit derived from the compound represented by the aforementioned formula (a4), in consideration of colorless transparency and heat resistance, the silane compound contained in the polyimide precursor composition of the present invention is preferably selected from A silane compound of at least one of the group consisting of the compound represented by the aforementioned general formula (2-1), the compound represented by the aforementioned general formula (2-3), and the compound represented by the aforementioned general formula (2-4), It is preferably at least one silane compound selected from the group consisting of the compound represented by the aforementioned general formula (2-3) and the compound represented by the aforementioned general formula (2-4), more preferably selected from the group consisting of At least one silane compound of the group consisting of compounds represented by the aforementioned general formula (2-3).

Also, when the constituent units derived from the compound represented by the aforementioned formula (a5) are included in the constituent unit AA, in consideration of colorless transparency and heat resistance, the silane compound contained in the polyimide precursor composition of the present invention is preferably At least one silane selected from the group consisting of the compound represented by the aforementioned general formula (2-2), the compound represented by the aforementioned general formula (2-3), and the compound represented by the aforementioned general formula (2-4) The compound is preferably at least one silane compound selected from the group consisting of the compound represented by the aforementioned general formula (2-2) and the compound represented by the aforementioned general formula (2-3), more preferably selected from A silane compound of at least one of the group consisting of compounds represented by the aforementioned general formula (2-3).

Structural unit AA may also contain structural units other than the aforementioned structural units. The tetracarboxylic dianhydride which provides such a structural unit is not specifically limited, An alicyclic tetracarboxylic dianhydride and an aliphatic tetracarboxylic dianhydride which provide structural units other than a structural unit (AA1) are mentioned. Examples of the alicyclic tetracarboxylic dianhydride providing structural units other than the structural unit (AA1) include 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 1,2,3,4-cyclohexane Butane tetracarboxylic dianhydride, dicyclohexyl tetracarboxylic dianhydride, etc. As an aliphatic tetracarboxylic dianhydride which provides the structural unit derived from an aliphatic tetracarboxylic dianhydride, 1,2,3,4- butane tetracarboxylic dianhydride etc. are mentioned. The structural unit arbitrarily contained in the structural unit AA may be one type, or two or more types. In addition, in this specification, an aromatic tetracarboxylic dianhydride means a tetracarboxylic dianhydride containing one or more aromatic rings, and an alicyclic tetracarboxylic dianhydride means a tetracarboxylic dianhydride containing one or more alicyclic rings and does not contain an aromatic ring. Cyclic tetracarboxylic dianhydrides, aliphatic tetracarboxylic dianhydrides mean tetracarboxylic dianhydrides containing neither aromatic rings nor alicyclic rings.

式(b1)中，X為選自於由單鍵、-NHCO-、-CONH-、-COO-及-OCO-構成之群組中之至少一者。 (Constituent unit BA) The structural unit BA is a structural unit derived from a diamine, and includes a structural unit (BA1) derived from a compound represented by formula (b1). When the structural unit (BA1) is included in the structural unit BA, it is excellent in heat resistance, and especially when combined with a silane compound, it is excellent in the effect of reducing yellowness. [chem 32]

In formula (b1), X is at least one member selected from the group consisting of a single bond, -NHCO-, -CONH-, -COO-, and -OCO-.

The structural unit (BA1) preferably contains a structural unit (BA11) derived from a compound represented by the following formula (b11). [chem 33]

式(b12)中，X為選自於由單鍵、-NHCO-、-CONH-、-COO-及-OCO-構成之群組中之至少一者。 Moreover, the structural unit (BA1) preferably contains a structural unit (BA12) derived from a compound represented by the following formula (b12). [chem 34]

In formula (b12), X is at least one member selected from the group consisting of a single bond, -NHCO-, -CONH-, -COO-, and -OCO-.

The constituent unit (BA12) comprises a constituent unit (BA121) derived from a compound represented by the following formula (b121), a constituent unit (BA122) derived from a compound represented by the following formula (b122), and a constituent unit (BA122) derived from a compound represented by the following formula (b123) At least one of the group consisting of the structural unit (BA123) of the compound, in consideration of heat resistance, preferably includes a structural unit (BA121) derived from a compound represented by the following formula (b121), more preferably derived from the following formula ( The structural unit (BA121) of the compound represented by b121). [chem 35]

The compound represented by the formula (b121) is 2,2'-bis(trifluoromethyl)benzidine (TFMB). By containing the structural unit (BA1) in the structural unit BA, it is excellent in heat resistance and the polyimide film with little change of the hue after heat processing can be obtained.

Structural unit BA may contain structural units other than structural unit (BA1). Diamines providing such structural units are not particularly limited, and examples include: 3,5-diaminobenzoic acid (3,5-DABA), 9,9-bis(4-aminophenyl) fluorine (BAFL) , 4-aminobenzoic acid-4-aminophenyl ester (4-BAAB), 1,4-phenylenediamine, p-xylylenediamine, 1,5-diaminonaphthalene, 2,2'-dimethyl Biphenyl-4,4'-diamine, 4,4'-diaminodiphenylmethane, 1,4-bis[2-(4-aminophenyl)-2-propyl]benzene, 2 ,2-bis(4-aminophenyl)hexafluoropropane, 4,4'-diaminobenzanilide, 1-(4-aminophenyl)-2,3-dihydro-1,3 ,3-Trimethyl-1H-inden-5-amine, α,α'-bis(4-aminophenyl)-1,4-diisopropylbenzene, N,N'-bis(4-amine phenyl) terephthalamide, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, and 1,4-bis(4-aminophenoxy)benzene, etc. Aromatic diamines other than compounds represented by formula (b1); alicyclic diamines such as 1,3-bis(aminomethyl)cyclohexane and 1,4-bis(aminomethyl)cyclohexane and aliphatic diamines such as ethylenediamine and hexamethylenediamine.

式(b2)表示之化合物為9,9-雙(4-胺基苯基)茀(BAFL)。 當構成單元BA包含構成單元(BA2)時，構成單元(BA1)與構成單元(BA2)之莫耳比[(BA1)/(BA2)]宜為50/50～90/10，較佳為50/50～80/20，更佳為50/50～70/30。 Among the structural units other than the structural unit (BA1), it is preferable to contain a structural unit (BA2) derived from a compound represented by the following formula (b2). [chem 36]

The compound represented by the formula (b2) is 9,9-bis(4-aminophenyl)fluorene (BAFL). When the constituent unit BA includes the constituent unit (BA2), the molar ratio [(BA1)/(BA2)] of the constituent unit (BA1) to the constituent unit (BA2) is preferably 50/50 to 90/10, preferably 50 /50～80/20, more preferably 50/50～70/30.

When the constituent unit BA includes the constituent unit (BA1) and the constituent unit (BA2), considering the viewpoint of colorless transparency and heat resistance, the silane compound contained in the polyimide precursor composition of the present invention is preferably selected from The silane compound of at least one of the group consisting of the compound represented by the aforementioned general formula (2-2), the compound represented by the aforementioned general formula (2-3), and the compound represented by the aforementioned general formula (2-4), is more It is preferably at least one silane compound selected from the group consisting of the compound represented by the aforementioned general formula (2-2) and the compound represented by the aforementioned general formula (2-3), more preferably selected from the group consisting of the aforementioned At least one silane compound of the group consisting of compounds represented by the general formula (2-3).

In addition, in this specification, an aromatic diamine means a diamine containing one or more aromatic rings, an alicyclic diamine means a diamine containing one or more alicyclic rings and no aromatic ring, and an aliphatic diamine Means a diamine containing neither an aromatic ring nor an aliphatic ring. The structural unit arbitrarily contained in the structural unit BA may be 1 type, and may be 2 or more types.

(Manufacturing method of polyimide precursor) The polyimide precursor contained in the polyimide precursor composition of this invention can be manufactured by making the said tetracarboxylic-acid component which provides a structural unit AA, and the diamine component which provides a structural unit BA react. That is, it can be produced by reacting the tetracarboxylic acid component providing the structural unit A and the diamine component providing the structural unit B described in the item of <each structural unit of polyimide>. In addition, the amount of the diamine component is preferably 0.9 to 1.1 mol with respect to the tetracarboxylic acid component.

The method of making a tetracarboxylic-acid component and a diamine component react in this manufacturing method is not specifically limited, A well-known method can be used. As far as the specific reaction method is concerned, adding tetracarboxylic acid components, diamine components, solvents, and optional end-capping agents into the reactor, and heating them at 0-120°C, preferably at 5-80°C The method of stirring for 1 to 72 hours in the range of 1 to 72 hours, etc. When it is reacted below 80°C, the molecular weight of the polyimide precursor will not vary depending on the temperature history during polymerization, and the progress of thermal imidization can also be suppressed, so the polyimide precursor can be stably produced. Polyimide precursor of amide acid.

By the above method, a polyimide precursor solution having a polyamic acid structure dissolved in a solvent can be obtained. The concentration of the polyimide precursor in the obtained solution is preferably 1-50% by mass, preferably 3-35% by mass, more preferably 5-30% by mass.

式(2-1)及式(2-4)中，R ¹及R ²各自獨立地為氫、碳數1～6之烷基、苯基、或碳數1～6之胺基烷基。式(2-1)、式(2-2)、式(2-3)及式(2-4)中，R ³為碳數1～6之烷基。 藉由含有該矽烷化合物，可獲得具耐熱性且低黃色度的薄膜。 考量無色透明性及耐熱性的觀點，本發明之聚醯亞胺前驅體組成物中含有的矽烷化合物宜為選自於由前述通式(2-2)表示之化合物、前述通式(2-3)表示之化合物及前述通式(2-4)表示之化合物構成之群組中之至少一者之矽烷化合物，較佳為選自於由前述通式(2-2)表示之化合物及前述通式(2-3)表示之化合物構成之群組中之至少一者之矽烷化合物，更佳為選自於由前述通式(2-3)表示之化合物構成之群組中之至少一者之矽烷化合物。 <Silane compound (silane compound contained in the polyimide precursor composition)> The silane compound contained in the polyimide precursor composition of the present invention is selected from the group represented by the following general formula (2-1): The compound represented by the following general formula (2-2), the compound represented by the following general formula (2-3), and the compound represented by the following general formula (2-4) constitute at least one silane compound . [chem 37]

In formula (2-1) and formula (2-4), R ¹ and R ² are each independently hydrogen, alkyl having 1 to 6 carbons, phenyl, or aminoalkyl having 1 to 6 carbons. In formula (2-1), formula (2-2), formula (2-3) and formula (2-4), R ³ is an alkyl group having 1 to 6 carbon atoms. By containing this silane compound, a thin film with heat resistance and low yellowness can be obtained. From the viewpoint of colorless transparency and heat resistance, the silane compound contained in the polyimide precursor composition of the present invention is preferably selected from the compounds represented by the aforementioned general formula (2-2), the aforementioned general formula (2- 3) The silane compound of at least one of the compound represented by the compound represented by the aforementioned general formula (2-4) and the group consisting of the compound represented by the aforementioned general formula (2-4), preferably selected from the group consisting of the compound represented by the aforementioned general formula (2-2) and the aforementioned At least one silane compound selected from the group consisting of compounds represented by the general formula (2-3), more preferably at least one selected from the group consisting of the compounds represented by the aforementioned general formula (2-3) of silane compounds.

In formula (2-1), R ¹ and R ² are each independently hydrogen, alkyl having 1 to 6 carbons, phenyl, or aminoalkyl having 1 to 6 carbons, preferably selected from the group consisting of hydrogen and at least one of the group consisting of phenyl, more preferably hydrogen. In formula (2-1), R ³ is an alkyl group having 1 to 6 carbon atoms, preferably at least one selected from the group consisting of methyl and ethyl, more preferably ethyl. In formula (2-2), R ³ is an alkyl group having 1 to 6 carbon atoms, preferably at least one selected from the group consisting of methyl and ethyl, more preferably ethyl. In formula (2-3), R ³ is an alkyl group having 1 to 6 carbon atoms, preferably at least one selected from the group consisting of methyl and ethyl, more preferably methyl. In the formula (2-4), R ¹ and R ² are each independently hydrogen, an alkyl group having 1 to 6 carbons, a phenyl group, or an aminoalkyl group having 1 to 6 carbons, preferably 1 to 6 carbons The alkyl group. In formula (2-4), R ³ is an alkyl group having 1 to 6 carbon atoms, preferably at least one selected from the group consisting of methyl and ethyl, more preferably ethyl.

The aforementioned silane compounds can be commercially available. As a preferred commercially available silane compound, Shin-Etsu Chemical Co., Ltd. KBE9007N (3-isocyanate propyl triethoxysilane, formula (2-2) The compound when R ³ is ethyl), KBM9659 (refer to - (trimethoxysilylpropyl) isocyanurate, the compound when R ³ is methyl in formula (2-3), KBM573 (N -Phenyl-3-aminopropyltrimethoxysilane, compound when R ³ is methyl in formula (2-1), KBE9103P (3-triethoxysilyl-N-(1,3- Dimethyl-butylene) propylamine, the compound when ^R3 is ethyl in formula (2-4), KBE903 (3-aminopropyltriethoxysilane, ^R3 in formula (2-1) is Compound when ethyl), KBM903 (3-aminopropyltrimethoxysilane, compound when R ³ is methyl in formula (2-1)), etc.

The content of the aforementioned silane compound relative to the polyimide precursor is preferably from 10 ppm to 50,000 ppm, preferably from 1,000 ppm to 20,000 ppm, more preferably from 2,000 ppm to 15,000 ppm, and more preferably from 3,000 ppm to 12,000 ppm It is not more than ppm, more preferably not less than 3,000 ppm and not more than 8,000 ppm. When the amount of the silane compound falls within this range, a thin film having heat resistance and little change in hue after heat treatment can be obtained. In addition, in this specification, "ppm" means mass parts per million.

[Varnish (varnish containing polyimide precursor composition)] The varnish of the present invention contains the aforementioned polyimide precursor composition and an organic solvent. That is, the polyimide precursor, the silane compound, and an organic solvent are contained, and the polyimide precursor and the silane compound are dissolved in the organic solvent. The organic solvent is not particularly limited as long as it can dissolve the polyimide precursor and the silane compound, and it is preferable to use the above-mentioned compounds as solvents used in the production of the polyimide precursor alone or in combination of two or more. The varnish of the present invention may be obtained by directly dissolving the silane compound in the above-mentioned polyimide precursor solution, or may be obtained by further mixing and dissolving the polyimide precursor solution with a dilution solvent and a silane compound. .

The varnish of the present invention may further contain a dehydration catalyst. Examples of the dehydration catalyst include acid anhydrides such as acetic anhydride, propionic anhydride, n-butyric anhydride, benzoic anhydride, and trifluoroacetic anhydride; carbodiimide compounds such as dicyclohexylcarbodiimide; and the like. These can be used individually or in combination of 2 or more types.

The polyimide precursor contained in the varnish of the present invention has solvent solubility, so it can be made into a stable high-concentration varnish at room temperature. The varnish of the present invention preferably contains 3-40% by mass of the polyimide precursor (polyamic acid), more preferably 5-30% by mass. The viscosity of the varnish should be 0.1-100Pa･s, more preferably 0.1-20Pa･s. The viscosity of the varnish is the value measured at 25°C with an E-type viscometer. In addition, the varnish of the present invention may also contain inorganic fillers, adhesion promoters, release agents, flame retardants, ultraviolet stabilizers, surfactants, leveling agents, Agents, defoamers, fluorescent whitening agents, crosslinking agents, polymerization initiators, photosensitizers and other additives. The manufacturing method of the varnish of this invention is not specifically limited, A well-known method can be used. For example, it can be obtained by mixing and dissolving the above-mentioned silane compound in the solution of the polyimide precursor obtained by the above-mentioned production method, and further mixing the solvent and adjusting the concentration as necessary.

[Polyimide film and method for producing polyimide film using polyimide precursor composition] The polyimide film of the present invention is preferably manufactured using the aforementioned varnish. The polyimide film of the present invention is obtained by imidizing the aforementioned polyimide precursor, and therefore contains a polyimide containing a repeating unit represented by the general formula (1).

The method of producing the polyimide film using the varnish of the present invention is not particularly limited, and known methods can be used. For example, the varnish of the present invention can be coated on a smooth support such as a glass plate, a metal plate, or plastic, or formed into a film, and then the reaction solvent, dilution solvent, etc. contained in the varnish can be removed by heating An organic solvent is used to obtain a polyamic acid film, and the polyamic acid in the polyamic acid film is imidized (dehydrated and ring-closed) by heating to produce a polyimide film. That is to say, the polyimide film of the present invention is preferably a film obtained by coating the aforementioned varnish on a support and heating it, and the manufacturing method of the polyimide film of the present invention is preferably coating the aforementioned varnish on a support Body and heating method.

The heating temperature when drying the varnish containing the polyimide precursor composition to obtain a polyimide precursor (polyamic acid) film is preferably 50 to 150°C. The heating temperature for imidizing the polyimide precursor by heating is preferably 350-450°C, more preferably 380-420°C. Moreover, heating time is normally 1 minute - 6 hours, Preferably it is 5 minutes - 2 hours, More preferably, it is 15 minutes - 1 hour. By setting such temperature and time, the physical properties of the polyimide film obtained will become favorable. The heating environment includes air, nitrogen, oxygen, hydrogen, nitrogen/hydrogen mixed gas, etc., but in order to suppress the coloring of the obtained polyimide resin, nitrogen with an oxygen concentration of 100ppm or less and a hydrogen concentration of 0.5% or less are preferred. Nitrogen/hydrogen gas mixture. In addition, the imidization method is not limited to thermal imidization, and chemical imidization can also be used.

The thickness of the polyimide film of the present invention can be appropriately selected depending on the application and the like, and is preferably at least 1 μm, preferably at least 5 μm, and more preferably at least 7 μm. Moreover, it is preferably 250 μm or less, preferably 100 μm or less, more preferably 50 μm or less, and still more preferably 20 μm or less. The thickness of the polyimide film can be easily controlled by adjusting the solid content concentration and viscosity of the varnish.

The glass transition temperature of the polyimide film of the present invention is preferably above 350°C, preferably above 380°C, more preferably above 400°C. When the glass transition temperature of the polyimide film is in the above-mentioned range, it has excellent heat resistance and little change in hue after heat treatment.

The polyimide film of the present invention can be ideally used as a film for various members such as color filters, flexible displays, semiconductor parts, and optical members. The polyimide film of the present invention can be ideally used as a substrate of image display devices such as liquid crystal displays and OLED displays. [Example]

Hereinafter, the present invention will be specifically described using examples. However, the present invention is not limited to these Examples. The various physical properties of the thin films obtained in Examples and Comparative Examples were measured by the methods shown below.

(1) Film thickness The film thickness was measured using a film thickness measuring device Filmetrics F20 (manufactured by Filmetrics Co., Ltd.).

(2) Total light transmittance, yellow index (YI) The total light transmittance and YI are measured in accordance with JIS K7136, YI ASTM E313-05 (D light source, 65°), using the color-turbidity simultaneous measuring device "COH7700" manufactured by Nippon Denshoku Kogyo Co., Ltd.

(3) Evaluation of laminated film In the same manner as the manufacturing process of a display for an image display device, a laminated film was manufactured, heat-treated, and the hue change after the heat treatment was visually evaluated. Laminate films were produced in the following manner. The polyimide films obtained in the examples and comparative examples were not peeled off, and a SiO film with a thickness of 300 nm was formed by sputtering on the polyimide film, and an ITO (indium tin oxide ₎ film with a thickness of 1230 nm was formed thereon. ) film, and annealed (heated) at 400°C for 1 hour. Whether the laminated film before and after annealing has yellowing (increase in the color density of the yellow system) is evaluated visually and according to the following criteria. None (no yellowing): No yellowing (no hue change) was observed in the laminated film before and after annealing. Yes (yellowing): Yellowing was observed in the laminated film before and after annealing (with a hue change). (No yellowing), the color change after heat treatment is small, and the system is good.

The tetracarboxylic-acid component and diamine component used in the Example and the comparative example, their abbreviation, etc. are as follows. <Tetracarboxylic acid component> CpODA: Norbornane-2-spiro-α-cyclopentanone-α'-spiro-2''-norbornane-5,5'',6,6''-tetracarboxylic acid Dianhydride (manufactured by ENEOS Co., Ltd.; compound represented by formula (a1)) s-BPDA: 3,3',4,4'-biphenyltetracarboxylic dianhydride (manufactured by Mitsubishi Chemical Co., Ltd., formula ( Compound represented by a4s)) BPAF: 9,9-bis(3,4-dicarboxyphenyl) stilbenic dianhydride (manufactured by JFE Chemical Co., Ltd.; compound represented by formula (a5)) <diamine component> TFMB: 2,2'-bis(trifluoromethyl)benzidine (manufactured by SEIKA Co., Ltd.; a compound represented by formula (b121)) BAFL: 9,9-bis(4-aminophenyl) fluorine (JFE Chemical ( stock) company; compound represented by formula (b2)) <silane compound> KBE9007N: 3-isocyanate propyltriethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., R ³ in formula (2-2) is B base compound) KBM9659: ginseng-(trimethoxysilylpropyl) isocyanurate (manufactured by Shin-Etsu Chemical Co., Ltd., compound when R ³ in formula (2-3) is a methyl group) KBM573 : N-phenyl-3-aminopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., ^R1 in formula (2-1) is phenyl, ^R2 is hydrogen atom, and ^R3 is methyl base compound) KBE9103P: 3-triethoxysilyl-N-(1,3-dimethyl-butylene) propylamine (manufactured by Shin-Etsu Chemical Co., Ltd., R ¹ in formula (2-4) is a methyl group, R ² is a butyl group, and R ³ is a compound when an ethyl group) KBE903: 3-Aminopropyltriethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., in formula (2-1) Compound when R ¹ and R ² are hydrogen atoms and R ³ is ethyl group) KBM903: 3-Aminopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., R 1 and R ³ in formula (2-1) Compound when R ² is a hydrogen atom and R ³ is a methyl group) TEOS: Tetraethoxysilane <Surface modifier> BYK-378: Polysiloxane-based surface modifier (manufactured by BYK Japan Co., Ltd.)

Abbreviations and the like of solvents and catalysts used in Examples and Comparative Examples are as follows. GBL: γ-butyrolactone (manufactured by Mitsubishi Chemical Co., Ltd.) TEA: Triethylamine (manufactured by Kanto Chemical Co., Ltd.) TEDA: Triethylenediamine (manufactured by Tokyo Chemical Industry Co., Ltd.)

<Example 1> TFMB 19.214g (0.060 mole ), BAFL 13.938g (0.040 moles), GBL 126.903g, and stirred at a speed of 200rpm at an internal temperature of 70°C under a nitrogen atmosphere to obtain a solution. After adding 23.063g (0.060 mol) of CpODA and 11.768g (0.040 mol) of s-BPDA to this solution, put in 31.726g of GBL and 0.506g of TEA as the imidization catalyst, and heat it with a heating bag for a period of time The temperature in the reaction system was increased to 190° C. in about 20 minutes. The distilled components were collected and the rotational speed was adjusted according to the increase in viscosity, while the temperature in the reaction system was kept at 190° C. and refluxed for 5 hours. Then, GBL was added so that the solid content concentration would become 10% by mass, and the temperature inside the reaction system was cooled to 120° C., and stirred for about 1 hour to make it homogenized, thereby obtaining a polyimide varnish.

KBE9007N was added to 100 g of the obtained varnish so that it reached 5000 ppm relative to polyimide, and BYK-378 was added so that it reached 1000 ppm relative to polyimide, and stirred for 30 minutes to make it homogeneous to obtain polyimide Composition varnish. Next, the obtained polyimide composition varnish was applied by spin coating on a glass plate (manufactured by AGC Co., Ltd., AN-100), and kept at 80° C. for 20 minutes on a hot plate, and then Move to a hot air dryer, raise the temperature to 400°C at a heating rate of 5°C/min under a nitrogen atmosphere, and heat at 400°C in a hot air dryer for 30 minutes under a nitrogen atmosphere to evaporate the solvent to obtain polyimide film. The evaluation results are shown in Table 1. In addition, all evaluations were performed in the state attached to the glass plate, and were the result including the glass plate.

<Examples 2 to 7 and Comparative Example 2> A polyimide film was obtained in the same manner as in Example 1 except that the silane compounds shown in Table 1 were used in the amounts shown in Table 1 instead of KBE9007N. The results are shown in Table 1. In addition, all evaluations were performed in the state attached to the glass plate, and were the result including the glass plate.

＜Comparative example 1＞ A polyimide film was obtained in the same manner as in Example 1 except that KBE9007N was not used. The results are shown in Table 1. In addition, all evaluations were performed in the state attached to the glass plate, and were the result including the glass plate.

<Example 8> TFMB 17.613g (0.055 mole ), BAFL 15.680g (0.045 moles), GBL 107.673g, and stirred at a speed of 200rpm at an internal temperature of 70°C under a nitrogen atmosphere to obtain a solution. After adding 34.594g (0.090 mol) of CpODA and 4.584g (0.010 mol) of BPAF to this solution, add 26.918g of GBL, 0.506g of TEA and 0.056g of TEDA as imidization catalysts, and heat with a heating pack , the temperature in the reaction system was increased to 190° C. for about 20 minutes. The distilled components were collected and the rotational speed was adjusted according to the increase in viscosity, while the temperature in the reaction system was kept at 190° C. and refluxed for 5 hours. Then, GBL was added so that the solid content concentration would become 10% by mass, and the temperature inside the reaction system was cooled to 120° C., and stirred for about 1 hour to make it homogenized, thereby obtaining a polyimide varnish.

KBE9007N was added to 100 g of the obtained varnish so that it reached 5000 ppm relative to polyimide, and BYK-378 was added so that it reached 1000 ppm relative to polyimide, and stirred for 30 minutes to make it homogeneous to obtain polyimide Composition varnish. Next, the obtained polyimide composition varnish was applied by spin coating on a glass plate (manufactured by AGC Co., Ltd., AN-100), and kept at 80° C. for 20 minutes on a hot plate, and then Move to a hot air dryer, raise the temperature to 400°C at a heating rate of 5°C/min under a nitrogen atmosphere, and heat at 400°C in a hot air dryer for 30 minutes under a nitrogen atmosphere to evaporate the solvent to obtain polyimide film. The evaluation results are shown in Table 1. In addition, all evaluations were performed in the state attached to the glass plate, and were the result including the glass plate.

<Examples 9 to 11 and Comparative Example 4> A polyimide film was obtained in the same manner as in Example 8 except that the silane compounds shown in Table 1 were used in the amounts shown in Table 1 instead of KBE9007N. The results are shown in Table 1. In addition, all evaluations were performed in the state attached to the glass plate, and were the result including the glass plate.

＜Comparative example 3＞ A polyimide film was obtained in the same manner as in Example 8 except that KBE9007N was not used. The results are shown in Table 1. In addition, all evaluations were performed in the state attached to the glass plate, and were the result including the glass plate.

[Table 1]

As shown in Table 1, it can be seen that the polyimide film obtained from the polyimide resin composition of the present invention has excellent heat resistance, and is also excellent in colorlessness after heat treatment, with little change in hue.

Claims (17)

A polyimide resin composition, comprising: a polyimide having a repeating unit represented by the following general formula (1), and a compound selected from compounds represented by the following general formula (2-1), the following general formula (2 A silane compound of at least one of the group consisting of compounds represented by -2), compounds represented by the following general formula (2-3), and compounds represented by the following general formula (2-4);

In the formula (1), ^X1 is a tetravalent group having an alicyclic structure or an aromatic ring having at least one norbornane skeleton, and X is selected from single bonds, -NHCO-, -CONH-, -COO At least one of the group consisting of - and -OCO-; In formula (2-1) and formula (2-4), R ¹ and R ² are each independently hydrogen, an alkyl group with 1 to 6 carbons, Phenyl, or an aminoalkyl group with 1 to 6 carbons; In formula (2-1), formula (2-2), formula (2-3) and formula (2-4), R ³ is carbon number 1 ~6 alkyl groups. The polyimide resin composition as claimed in claim 1, wherein the repeating unit represented by the general formula (1) is a repeating unit represented by the following general formula (1-2);

In the formula (1-2), X ^is a 4-valent group having an alicyclic structure or an aromatic ring having at least one norbornane skeleton, and X is selected from single bonds, -NHCO-, -CONH-, At least one of the group consisting of -COO- and -OCO-. The polyimide resin composition according to claim 1 or 2, wherein X in the formula (1) is a single bond. The polyimide resin composition as any one of claims 1 to 3, wherein, ^X in the formula (1) is selected from the following formula (3), the following formula (4), the following formula ( 5), at least one of the group formed by the following formula (6) and the following formula (7);

In formula (5), W is at least one selected from the group consisting of a single bond and an organic group with 1 to 16 carbons; in formula (6), Z is selected from a group consisting of a single bond, carbon number At least one of the group consisting of 1-13 organic groups; In formula (7), R is each independently methyl or trifluoromethyl, m is 1 or 2, and n is an integer of 0-4. The polyimide resin composition as any one of claims 1 to 4, wherein, ^X in the formula (1) is selected from the following formula (8), the following formula (9) and the following formula ( 10) At least one of the groups formed;

. The polyimide resin composition according to any one of claims 1 to 5, wherein the repeating unit represented by the formula (1) is at least 10 mol% relative to all repeating units of the polyimide. The polyimide resin composition according to any one of claims 1 to 6, wherein the total content of the silane compounds is not less than 10 ppm and not more than 50,000 ppm relative to the polyimide. A varnish comprising the polyimide resin composition according to any one of claims 1 to 7 and an organic solvent. A polyimide film obtained by coating the varnish according to Claim 8 on a support and heating it. The polyimide film according to Claim 9, wherein the glass transition temperature of the polyimide film is above 350°C. A method for producing a polyimide film, characterized by: coating the varnish according to claim 8 on a support and heating it. A polyimide precursor composition, containing: a polyimide precursor having a repeating unit represented by the following general formula (11), and being selected from compounds represented by the following general formula (2-1), the following general formula A silane compound of at least one of the group consisting of the compound represented by the formula (2-2), the compound represented by the following general formula (2-3), and the compound represented by the following general formula (2-4);

In formula (11), ^X2 is a tetravalent group having an alicyclic structure or an aromatic ring having at least one norbornane skeleton, and ^R4 and ^R5 are each independently hydrogen, an alkyl group having 1 to 6 carbon atoms , an alkylsilyl group with 3 to 9 carbon atoms, X is at least one selected from the group consisting of a single bond, -NHCO-, -CONH-, -COO- and -OCO-; formula (2- 1) and formula (2-4), R ¹ and R ² are each independently hydrogen, alkyl with 1 to 6 carbons, phenyl, or aminoalkyl with 1 to 6 carbons; formula (2- 1), in formula (2-2), formula (2-3) and formula (2-4), R ³ is an alkyl group having 1 to 6 carbon atoms. The polyimide precursor composition according to claim 12, wherein the total content of the silane compounds is not less than 10 ppm and not more than 50,000 ppm relative to the polyimide precursor. A varnish containing the polyimide precursor composition and organic solvent as claimed in claim 12 or 13. A polyimide film obtained by coating the varnish according to Claim 14 on a support and heating it. The polyimide film according to claim 15, wherein the glass transition temperature of the polyimide film is above 350°C. A method for producing a polyimide film, which is characterized by: coating the varnish according to claim 14 on a support and heating it.