TW202219122A - Polymer composition, varnish, and polyimide film - Google Patents

Abstract

A polymer composition containing a polymer (X) that contains at least one repeating unit selected from the group consisting of repeating units represented by general formula (1) shown below and repeating units represented by general formula (2) shown below, and a compound (Y) represented by general formula (3) below. (In formula (1), X ¹represents a tetravalent group containing an alicyclic structure or an aromatic ring. In formula (2), X ²represents a tetravalent group containing an alicyclic structure or an aromatic ring, and R ¹and R ²each independently represent a hydrogen atom, an alkyl group of 1 to 6 carbon atoms, or an alkylsilyl group of 3 to 9 carbon atoms. In formula (3), R ³is at least one group selected from the group consisting of alkyl groups of 1 to 30 carbon atoms, a phenyl group, alkoxy groups, an acryloyl group, a methacryloyl group, an acryloyloxyethyl group and a methacryloyloxyethyl group, and n is an integer of 0 to 2).

Description

Polymer Compositions, Varnishes, and Polyimide Films

The present invention relates to polymer compositions, varnishes, and polyimide films.

Since polyimide resins have excellent mechanical properties and heat resistance, various applications in the fields of electrical and electronic parts have been studied. For example, polyimide film substrates are expected to replace glass substrates used in image display devices such as liquid crystal displays and OLED displays, and development of polyimide resins that satisfy the performance as an optical material is underway. However, in recent years, due to the high functionalization of electronic devices, electronic components are required to satisfy various required performances at the same time. Therefore, for the polyimide resin used in the display, there are also attempts to add new properties to the original properties of the resin by blending various additives, and to improve the original properties.

For example, Patent Document 1 discloses a polyimide precursor composition containing a specific polyimide and a specific phosphorus for the purpose of preventing crystallization and shortening the layer formation time in addition to heat resistance and mechanical properties. The compound; the above-mentioned polyimide, can produce a polyimide film having a large water vapor transmission coefficient by performing heat treatment under the condition that the maximum heating temperature is set at 300 to 500°C. In addition, Patent Document 2 discloses a polyimide precursor composition containing a polyimide having a specific repeating unit for the purpose of obtaining a polyimide having transparency, heat resistance, and low coefficient of thermal expansion. Amine precursors, and phosphorus compounds containing phosphorus atoms and having a boiling point at 1 atm below the decomposition temperature and below 350°C. [Prior Art Literature] [Patent Literature]

Patent Document 1: International Publication No. 2016/121817 Patent Document 2: International Publication No. 2015/080139

[The problem to be solved by the invention]

As described above, a polyimide film is required to replace the glass substrate, and not only mechanical properties and heat resistance, but also high colorless transparency is required. However, it is difficult to have these properties together, and even if the heat resistance is improved by blending additives, it is difficult to prevent yellowing and the like. In addition, in order to exhibit colorless transparency in 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, for example, in the process of manufacturing a TFT in the manufacture of a display, under severe conditions of 350° C. or higher, the aliphatic diamine is less rigid than the aromatic diamine, so it is not easy to exhibit heat resistance. The colorless transparency of the lower fluorinated diamine is also impaired. Therefore, a polyimide film with excellent heat resistance and low yellowness is particularly required. The present invention has been made in view of such a situation, and an object of the present invention is to provide a polymer composition capable of obtaining a polyimide film with excellent heat resistance and low yellowness, a varnish containing the composition, and excellent heat resistance. , Polyimide film with low yellowness. [Means of Solving Problems]

The inventors of the present application found that a polymer composition comprising: a polymer containing repeating units derived from a tetracarboxylic acid having a specific fluorine-containing diamine and an alicyclic structure or an aromatic ring, and a specific phosphorus compound can solve the problem The above-mentioned problems lead to the completion of the invention.

(式(1)中，X ¹為具有脂環結構或芳香族環之4價之基。 式(2)中，X ²為具有脂環結構或芳香族環之4價之基，R ¹及R ²各自獨立地為氫、碳數1～6之烷基、或碳數3～9之烷基矽基。 式(3)中，R ³為選自於由碳數1～30之烷基、苯基、烷氧基、丙烯醯基、甲基丙烯醯基、丙烯醯氧乙基、及甲基丙烯醯氧乙基構成之群組中之至少一種，n為0～2。) ［2］如上述［1］之聚合物組成物，其中，相對於上述聚合物(X)之全部重複單元，上述式(1)表示之重複單元為10莫耳%以上。 ［3］如上述［1］或［2］之聚合物組成物，其中，相對於上述聚合物(X)之全部重複單元，上述式(2)表示之重複單元為10莫耳%以上。 ［4］如上述［1］～［3］中任一項之聚合物組成物，其中，相對於聚合物(X)，化合物(Y)之含量為10ppm以上且10,000ppm以下。 ［5］一種清漆，係藉由將如上述［1］至［4］中任一項之聚合物組成物溶解在有機溶劑中而形成的。 ［6］一種聚醯亞胺薄膜，係在支持體上塗布如上述［5］之清漆並加熱而獲得。 ［7］一種聚醯亞胺薄膜之製造方法，係在支持體上塗布如上述［5］之清漆。 [發明之效果] That is, the present invention relates to the following [1] to [7]. [1] A polymer composition comprising: a polymer containing at least one selected from the group consisting of a repeating unit represented by the following general formula (1) and a repeating unit represented by the following general formula (2) (X), and a compound (Y) represented by the following general formula (3). [hua 1]

(In formula (1), X ¹ is a tetravalent group having an alicyclic structure or an aromatic ring. In formula (2), X ² is a tetravalent group having an alicyclic structure or an aromatic ring, R ¹ and R ² is each independently hydrogen, an alkyl group having 1 to 6 carbon atoms, or an alkylsilyl group having 3 to 9 carbon atoms. In formula (3), R ³ is selected from an alkyl group having 1 to 30 carbon atoms. , at least one of the group consisting of phenyl, alkoxy, acryl, methacryloyl, acryloxyethyl, and methacryloyloxyethyl, and n is 0 to 2.) [2 ] The polymer composition according to the above [1], wherein the repeating unit represented by the above formula (1) is 10 mol % or more relative to all the repeating units of the above polymer (X). [3] The polymer composition according to the above [1] or [2], wherein the repeating unit represented by the above formula (2) is 10 mol % or more relative to all the repeating units of the above polymer (X). [4] The polymer composition according to any one of the above [1] to [3], wherein the content of the compound (Y) is 10 ppm or more and 10,000 ppm or less with respect to the polymer (X). [5] A varnish formed by dissolving the polymer composition according to any one of the above [1] to [4] in an organic solvent. [6] A polyimide film obtained by coating the varnish of the above [5] on a support and heating. [7] A method for producing a polyimide film, comprising coating the varnish of the above [5] on a support. [Effect of invention]

According to the present invention, a polymer composition capable of obtaining a polyimide film with excellent heat resistance and low yellowness, a varnish containing the composition, and a polyimide film with excellent heat resistance and low yellowness can be provided.

(式(1)中，X ¹為具有脂環結構或芳香族環之4價之基。 式(2)中，X ²為具有脂環結構或芳香族環之4價之基，R ¹及R ²各自獨立地為氫、碳數1～6之烷基、或碳數3～9之烷基矽基。 式(3)中，R ³為選自於由碳數1～30之烷基、苯基、烷氧基、丙烯醯基、甲基丙烯醯基、丙烯醯氧乙基、及甲基丙烯醯氧乙基構成之群組中之至少一種，n為0～2。) [Polymer composition] The polymer composition of the present invention contains at least one selected from the group consisting of a repeating unit represented by the following general formula (1) and a repeating unit represented by the following general formula (2) The polymer (X), and the compound (Y) represented by the following general formula (3). [hua 2]

(In formula (1), X ¹ is a tetravalent group having an alicyclic structure or an aromatic ring. In formula (2), X ² is a tetravalent group having an alicyclic structure or an aromatic ring, R ¹ and R ² is each independently hydrogen, an alkyl group having 1 to 6 carbon atoms, or an alkylsilyl group having 3 to 9 carbon atoms. In formula (3), R ³ is selected from an alkyl group having 1 to 30 carbon atoms. , at least one of the group consisting of phenyl, alkoxy, acryl, methacryloyl, acryloxyethyl, and methacryloyloxyethyl, and n is 0-2.)

The polymer composition of the present invention is excellent as a raw material for a polyimide film, and the reason why the obtained polyimide film has excellent properties such as excellent heat resistance and low yellowness is not clear, but it is considered as follows. The polymer composition of the present invention contains a specific phosphorus compound, and it is considered that the phosphorus compound is coordinated to the end of the polyimide obtained by imidizing the polymer, or that the end of the polyimide and the phosphorus are coordinated. The compound reacts to suppress side reactions, decomposition and deterioration of the terminal especially at high temperature, and also suppresses desorption of fluorine derived from the fluorine-containing diamine. Therefore, it is considered that both heat resistance and low yellowness can be achieved.

(式(1)中，X ¹為具有脂環結構或芳香族環之4價之基。 式(2)中，X ²為具有脂環結構或芳香族環之4價之基，R ¹及R ²各自獨立地為氫、碳數1～6之烷基、或碳數3～9之烷基矽基。) <Polymer (X)> The polymer (X) contained in the polymer composition of the present invention contains a repeating unit selected from the group consisting of repeating units represented by the following general formula (1) and repeating units represented by the following general formula (2). At least one of the group consisting of units. [hua 3]

(In formula (1), X ¹ is a tetravalent group having an alicyclic structure or an aromatic ring. In formula (2), X ² is a tetravalent group having an alicyclic structure or an aromatic ring, R ¹ and R ² is each independently hydrogen, an alkyl group having 1 to 6 carbon atoms, or an alkylsilyl group having 3 to 9 carbon atoms.)

(式(1-1)中，X ¹為具有脂環結構或芳香族環之4價之基。) The repeating unit represented by the aforementioned general formula (1) contained in the polymer (X) is preferably a repeating unit represented by the following general formula (1-1). [hua 4]

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

(式(2-1)中，X ²為具有脂環結構或芳香族環之4價之基，R ¹及R ²各自獨立地為氫、碳數1～6之烷基、或碳數3～9之烷基矽基。) The repeating unit represented by the aforementioned general formula (2) contained in the polymer (X) is preferably a repeating unit represented by the following general formula (2-1). [hua 5]

(In formula (2-1), X ² is a tetravalent group having an alicyclic structure or an aromatic ring, and R ¹ and R ² are each independently hydrogen, an alkyl group having 1 to 6 carbon atoms, or an alkyl group having 3 carbon atoms. ~9 alkylsilyl groups.)

(式(1)中，X ¹為具有脂環結構或芳香族環之4價之基。式(3)中，R ³為選自於由碳數1～30之烷基、苯基、烷氧基、丙烯醯基、甲基丙烯醯基、丙烯醯氧乙基、及甲基丙烯醯氧乙基構成之群組中之至少一種，n為0～2。) 亦可以係一種聚醯胺酸組成物，含有：含有下述通式(2)表示之重複單元的聚醯胺酸、及下述通式(3)表示之化合物(Y)。 [化7]

(式(2)中，X ²為具有脂環結構或芳香族環之4價之基，R ¹及R ²各自獨立地為氫、碳數1～6之烷基、或碳數3～9之烷基矽基。式(3)中，R ³為選自於由碳數1～30之烷基、苯基、烷氧基、丙烯醯基、甲基丙烯醯基、丙烯醯氧乙基、及甲基丙烯醯氧乙基構成之群組中之至少一種，n為0～2。) The polymer (X) contains at least one selected from the group consisting of the repeating unit represented by the above-mentioned general formula (1) and the repeating unit represented by the above-mentioned general formula (2), or may contain only the above-mentioned general formula (1) ), or either of the repeating units represented by the general formula (2) above, or both may be included. That is, the polymer composition of the present invention may be a polyimide composition comprising: a polyimide containing a repeating unit represented by the following general formula (1), and a compound represented by the following general formula (3) (Y), [Chemical 6]

(In formula (1), X ¹ is a tetravalent group having an alicyclic structure or an aromatic ring. In formula (3), R ³ is selected from the group consisting of an alkyl group having 1 to 30 carbon atoms, a phenyl group, and an alkane group. at least one selected from the group consisting of oxy, acryl, methacryloyl, acryloxyethyl, and methacryloyloxyethyl, and n is 0 to 2.) It can also be a polyamide The acid composition contains a polyamic acid containing a repeating unit represented by the following general formula (2), and a compound (Y) represented by the following general formula (3). [hua 7]

(In formula (2), X ² is a tetravalent group having an alicyclic structure or an aromatic ring, and R ¹ and R ² are each independently hydrogen, an alkyl group having 1 to 6 carbon atoms, or an alkyl group having 3 to 9 carbon atoms. In formula (3), R ³ is selected from the group consisting of an alkyl group having 1 to 30 carbon atoms, a phenyl group, an alkoxy group, a acryloyl group, a methacryloyl group, and a acryloyloxyethyl group. , and at least one of the group consisting of methacryloyloxyethyl, n is 0-2.)

The polymer (X) preferably contains the repeating unit represented by the above-mentioned general formula (1), and more preferably contains both the repeating unit represented by the above-mentioned general formula (1) and the repeating unit represented by the above-mentioned general formula (2).

In the above formula (1), X ¹ is a tetravalent group having an alicyclic structure or an aromatic ring. X ¹ is preferably obtained by removing two dianhydride moieties (four carboxyl moieties) from the tetracarboxylic dianhydride used as a raw material for the structural unit A derived from the tetracarboxylic dianhydride described later. In the above formula (2), X ² is a tetravalent group having an alicyclic structure or an aromatic ring. X ² is preferably obtained by removing two dianhydride moieties (four carboxyl moieties) from the tetracarboxylic dianhydride used as a raw material for the structural unit A derived from the tetracarboxylic dianhydride described later. In the above formula (2), R ¹ and R ² are each independently hydrogen, an alkyl group having 1 to 6 carbon atoms, or an alkylsilyl group having 3 to 9 carbon atoms, preferably hydrogen.

(Structure of Polymer (X)) As described above, the polymer (X) may contain at least one selected from the group consisting of the repeating unit represented by the above-mentioned general formula (1) and the repeating unit represented by the above-mentioned general formula (2), and may contain only the above-mentioned general formula Either the repeating unit represented by the formula (1) or the repeating unit represented by the general formula (2) above may contain both, and in particular, from the viewpoint of reducing yellowness and improving transparency, compared with the above-mentioned polymerization All repeating units of the substance (X), the repeating units represented by the above formula (1) are preferably 10 mol% or more, preferably 30 mol% or more, more preferably 50 mol% or more, and 70 mol% or more. More preferably, it is more than 90 mol%, even more preferably, it is less than 100 mol%. In addition, from the viewpoint of improving heat resistance while maintaining low yellowness, the repeating unit represented by the above formula (2) is preferably 10 mol% or more relative to all repeating units of the above polymer (X). More preferably 30 mol % or more, more preferably 50 mol % or more, still more preferably 70 mol % or more, still more preferably 90 mol % or more, and 100 mol % or less. Further, when both the repeating unit represented by the above general formula (1) and the repeating unit represented by the above general formula (2) are contained, the repeating unit represented by the above general formula (1) and the repeating unit represented by the above general formula (2) repeat The molar ratio of the unit [(1)/(2)] is preferably 10/90 to 70/30, preferably 20/80 to 60/40, and more preferably 25/75 to 55/45.

<Each structural unit of polymer (X)> A polymer (X) containing at least one selected from the group consisting of a repeating unit represented by the aforementioned general formula (1) and a repeating unit represented by the aforementioned general formula (2), and the structural units constituting the polymer are described below .

The polymer (X) has structural unit A derived from tetracarboxylic dianhydride and structural unit B derived from diamine. In addition, although in the repeating unit represented by the above general formula (1), the structural unit A and the structural unit B will form an imide structure, in the repeating unit represented by the above general formula (2) the structural unit A and the structural unit B will be In the formation of an amide acid structure, the structural unit derived from tetracarboxylic dianhydride is collectively referred to as structural unit A, and the structural unit derived from diamine is collectively referred to as structural unit B.

(structural unit A) Structural unit A is a structural unit derived from tetracarboxylic dianhydride, and is at least selected from the group consisting of a structural unit derived from alicyclic tetracarboxylic dianhydride and a structural unit derived from aromatic tetracarboxylic dianhydride One, from the viewpoint of low yellowness and transparency, is preferably a structural unit derived from an alicyclic tetracarboxylic dianhydride, and from the viewpoint of heat resistance, preferably a structural unit derived from an aromatic tetracarboxylic dianhydride .

式(a1)表示之化合物，為降莰烷-2-螺-α-環戊酮-α’-螺-2’’-降莰烷-5,5’’,6,6’’-四羧酸二酐。 Examples of alicyclic tetracarboxylic dianhydrides that provide structural units derived from alicyclic tetracarboxylic dianhydrides include 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 1,2,3,4 -Cyclobutanetetracarboxylic dianhydride, norbornane-2-spiro-α-cyclopentanone-α'-spiro-2''-norbornane-5,5'',6,6''-tetra Carboxylic dianhydride, Bicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, Dicyclohexyltetracarboxylic dianhydride, 5,5'-(1,4- phenylene)-bis[hexahydro-4,7-methylisobenzofuran-1,3-dione], 5,5'-bis-2-norbornene-5,5',6,6' -Tetracarboxylic acid-5,5',6,6'-dianhydride, or their positional isomers, etc. Among these, from the viewpoint of low yellowness and transparency, the compound represented by the following formula (a1) is preferable, and the structural unit A preferably contains the structural unit (A1) derived from the compound represented by the formula (a1). [hua 8]

The compound represented by formula (a1) is norbornane-2-spiro-α-cyclopentanone-α'-spiro-2''-norbornane-5,5'',6,6''-tetracarboxylate acid dianhydride.

Aromatic tetracarboxylic dianhydrides that provide structural units derived from aromatic tetracarboxylic dianhydrides, such as biphenyl tetracarboxylic dianhydride (BPDA), 9,9-bis(3,4-dicarboxyphenyl) fluoride Diacid Anhydride (BPAF), Pyromelic Acid Dianhydride, 3,3',4,4'-(hexafluoroisopropylidene)diphthalic anhydride, 3,3',4,4'-diphenyl Tetracarboxylic dianhydride, 3,3',4,4'-diphenylketone tetracarboxylic dianhydride, 2,2',3,3'-diphenylketone tetracarboxylic dianhydride, etc. Among these, from the viewpoint of having both heat resistance and low yellowness, at least one selected from the group consisting of a compound represented by the following formula (a2) and a compound represented by the following formula (a3) is preferable , preferably a compound represented by the following formula (a2). That is, the structural unit A preferably contains at least one selected from the group consisting of the structural unit (A2) derived from the compound represented by the following formula (a2) and the structural unit (A3) derived from the compound represented by the following formula (a3). , preferably contains a structural unit (A2) derived from a compound represented by the following formula (a2). [Chemical 9]

The compound represented by formula (a2) is biphenyltetracarboxylic dianhydride (BPDA), and a specific example thereof can be exemplified by 3,3',4,4'-biphenyltetracarboxylic dianhydride (s) represented by the following formula (a2s). -BPDA), 2,3,3',4'-biphenyltetracarboxylic dianhydride (a-BPDA) represented by the following formula (a2a), 2,2',3,3' represented by the following formula (a2i) - Biphenyltetracarboxylic dianhydride (i-BPDA). Among them, it is preferably 3,3',4,4'-biphenyltetracarboxylic dianhydride (s-BPDA) represented by the following formula (a2s). [Chemical 10]

The compound represented by formula (a3) is 9,9'-bis(3,4-dicarboxyphenyl)perylene anhydride (BPAF).

The structural unit A may contain structural units other than the aromatic tetracarboxylic dianhydride and the alicyclic tetracarboxylic dianhydride. The tetracarboxylic dianhydride that provides such a structural unit is not particularly limited, and examples thereof include aliphatic tetracarboxylic dianhydrides such as 1,2,3,4-butanetetracarboxylic dianhydride. The structural unit arbitrarily contained in the structural unit A may be one type or two or more types. In addition, in this specification, aromatic tetracarboxylic dianhydride means tetracarboxylic dianhydride containing one or more aromatic rings; alicyclic tetracarboxylic dianhydride means containing one or more alicyclic rings and does not Tetracarboxylic dianhydride containing aromatic ring; Aliphatic tetracarboxylic dianhydride means tetracarboxylic dianhydride containing neither aromatic ring nor alicyclic ring.

(Structural unit B) The structural unit B is a structural unit derived from a diamine, and contains a structural unit (B1) derived from the compound represented by the formula (b1). Since the structural unit (B1) is contained in the structural unit B, it is excellent in heat resistance, and especially when combined with the compound (Y), the effect of reducing the yellowness is excellent. The ratio of the structural unit (B1) in the structural unit B is preferably 45 mol % or more, preferably 70 mol % or more, more preferably 90 mol % or more, and particularly 99 mol % or more good. The upper limit of the ratio is not particularly limited, but is 100 mol % or less. [Chemical 11]

The structural unit (B1) preferably contains the structural unit (B11) derived from the compound represented by the following formula (b11). The structural unit (B1) is preferably a structural unit (B11) derived from a compound represented by the following formula (b11). [Chemical 12]

The compound represented by the formula (b11) is 2,2'-bis(trifluoromethyl)-4,4'-diaminediphenyl ether (6FODA). When the structural unit (B11) is contained in the structural unit B, especially in combination with the compound (Y), the effect of reducing the yellowness is excellent.

The structural unit B may contain structural units other than the structural unit (B1). The diamine that provides such a structural unit is not particularly limited, and examples thereof include 4-aminophenyl-4-aminobenzoic acid (4-BAAB), 3,5-diaminobenzoic acid (3,5-DABA) ), 9,9-bis(4-aminophenyl) fluoride, 1,4-phenylenediamine, p-xylylenediamine, 1,5-diaminenaphthalene, 2,2'-dimethyl Biphenyl-4,4'-diamine, 2,2'-dimethylbiphenyl-4,4'-diamine, 4,4'-diaminediphenylmethane, 1,4-bis[2-( 4-Aminophenyl)-2-propyl]benzene, 2,2-bis(4-aminophenyl)hexafluoropropane, 4,4'-diaminobenzylaminobenzene, 1-(4-amine Phenyl)-2,3-dihydro-1,3,3-trimethyl-1H-inden-5-amine, α,α'-bis(4-aminophenyl)-1,4-diisopropyl Benzene, N,N'-bis(4-aminophenyl)p-benzamide, 2,2-bis(3-amino-4-hydroxybenzene)hexafluoropropane, and 1,4-bis(4-amine Aromatic diamines such as phenoxy)benzene; alicyclic diamines such as 1,3-bis(aminomethyl)cyclohexane and 1,4-bis(aminomethyl)cyclohexane; and ethylenediamine And aliphatic diamines such as hexamethylene diamine.

式(b2)表示之化合物，為4-胺苯基-4-胺基苯甲酸(4-BAAB)。 Among these, the compound represented by the following formula (b2) is preferable, and the structural unit B preferably contains the structural unit (B2) derived from the compound represented by the formula (b2). [Chemical 13]

The compound represented by formula (b2) is 4-aminophenyl-4-aminobenzoic acid (4-BAAB).

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; an aliphatic diamine means a diamine containing no aromatic ring. Diamine means a diamine which contains neither aromatic ring nor alicyclic ring. The structural unit arbitrarily contained in the structural unit B may be one type or two or more types.

(Production method of polymer (X)) The polymer (X) can be produced by any method, but the following method is preferable. As described above, the polymer (X) contains any one of the repeating unit represented by the general formula (1) (ie, the amide moiety) and the repeating unit (ie, the amide moiety) represented by the aforementioned general formula (2). One, or both, can be adjusted by changing the manufacturing method. Specifically, in the production method when both the repeating unit represented by the formula (1) and the repeating unit represented by the formula (2) are contained (the production method of the imide-amide acid copolymer), by only Using the step of producing a moiety (polyimide moiety) mainly containing the repeating unit represented by the formula (1), a polymer (X) substantially composed of the repeating unit represented by the formula (1) (polyimide moiety) can be obtained. amine); by using only the step of producing a moiety (polyamic acid moiety) mainly containing the recurring unit represented by the formula (2), a polymer substantially composed of the recurring unit represented by the formula (2) can be obtained ( X) (polyamic acid).

The polymer (X) containing both the repeating unit represented by the formula (1) and the repeating unit represented by the formula (2) (hereinafter also referred to as an imine-amide acid copolymer), it is preferable to use the following steps. 1 and the method of step 2. Step 1: A step of obtaining an imine oligomer by reacting a tetracarboxylic acid component and a diamine component constituting an imide moiety Step 2: The step of reacting the imine oligomer obtained in the step 1 with the tetracarboxylic acid component and the diamine component constituting the amide acid part to obtain an imine-amide acid copolymer

Moreover, the polymer (X) (polyimide) which consists of the repeating unit represented by Formula (1) substantially can be obtained by making all tetracarboxylic-acid components and diamine components react in step 1. Specifically, in the production method of the polymer (X) (polyimide) substantially composed of the repeating unit represented by the formula (1), the above-mentioned step 1 is interpreted as "to make the tetracarboxylic acid constituting the polyimide A step of reacting a component with a diamine component to obtain a polyimide". In addition, without performing step 1, by reacting all the tetracarboxylic acid components and diamine components in step 2, a polymer (X) substantially composed of the repeating unit represented by the formula (2) (polyamic acid) can be obtained ). Specifically, in the method for producing the polymer (X) (polyamic acid) substantially composed of the repeating unit represented by the formula (2), the above-mentioned step 2 is interpreted as "to make the tetracarboxylic acid constituting the polyamic acid" The step of reacting the component with the diamine component to obtain the polyamide”.

〔step 1〕 Step 1 is a step of obtaining an imine oligomer by reacting a tetracarboxylic acid component and a diamine component constituting an imine moiety. The tetracarboxylic acid component used in the step 1 preferably contains the compound providing the structural unit (A1), and the entire amount thereof is preferably used in the step 1, and may contain a tetracarboxylic acid component other than the compound providing the structural unit (A1). The tetracarboxylic acid component other than the compound that provides the structural unit (A1) is preferably the compound that provides the structural unit (A2) or the compound that provides the structural unit (A3). The diamine component used in Step 1 preferably contains a compound that provides the structural unit (B1), and may contain a diamine component other than the compound that provides the structural unit (B1) within a range that does not impair the effects of the present invention. The tetracarboxylic acid component other than the compound that provides the structural unit (B1) is preferably the compound that provides the structural unit (B2). In step 1, the amount of the diamine component relative to the tetracarboxylic acid component is preferably 1.01-2 mol, preferably 1.05-1.9 mol, and more preferably 1.1-1.7 mol. Moreover, when obtaining the polymer (X) (polyimide) which consists of the repeating unit represented by Formula (1) substantially, it is preferable that the diamine component is 0.9-1.1 mol with respect to the tetracarboxylic acid component.

The method of reacting the tetracarboxylic acid component and the diamine component in order to obtain the imide oligomer in Step 1 is not particularly limited, and a known method can be used. The specific reaction method can be exemplified as follows: (1) Load the tetracarboxylic acid component, the diamine component and the reaction solvent into the reactor, stir at 10 to 110 ° C for 0.5 to 30 hours, then heat up and carry out the imidization reaction. Method, (2) After the diamine component and the reaction solvent are charged into the reactor and dissolved, the tetracarboxylic acid component is charged, and the temperature is stirred at 10 to 110 ° C for 0.5 to 30 hours as required, and then the temperature is raised and imidization is carried out. The reaction method, (3) the method of charging the tetracarboxylic acid component, the diamine component and the reaction solvent into the reactor, directly raising the temperature, and carrying out the imidization reaction, etc.

The imidization reaction is preferably performed using a Dean-Stark apparatus or the like while removing water generated during production. By performing such an operation, the polymerization degree and the imidization rate can be further improved.

A known imidization catalyst can be used in the above-mentioned imidization reaction. As the imidization catalyst, an alkali catalyst or an acid catalyst can be exemplified. Alkali catalyst, such as pyridine, quinoline, isoquinoline, α-picoline, β-picoline, 2,4-lutidine, 2,6-lutidine, trimethylamine, triethylamine, tripropylamine , Tributylamine, triethylenediamine, imidazole, N,N-dimethylaniline, N,N-diethylaniline and other organic base catalysts, potassium hydroxide and sodium hydroxide, potassium carbonate, sodium carbonate, carbonic acid Inorganic alkali catalysts such as potassium hydrogen and sodium bicarbonate. In addition, as the acid catalyst, crotonic acid, acrylic acid, trans-3-hexenoic acid, cinnamic acid, benzoic acid, toluic acid, oxybenzoic acid, terephthalic acid, benzenesulfonic acid, p-toluenesulfonic acid can be exemplified. acid, naphthalene sulfonic acid, etc. The above-mentioned imidization catalysts can be used alone or in combination of two or more. Among the above, from the viewpoint of operability, an alkali catalyst is preferable, an organic alkali catalyst is more preferable, one or more kinds selected from triethylamine and triethylenediamine are more preferable, and triethylamine is more preferable. Ethylamine.

The temperature of the imidization reaction is preferably 120 to 250°C, more preferably 160 to 200°C, from the viewpoints of the reaction rate and inhibition of gelation. In addition, the reaction time is preferably 0.5 to 10 hours after the start of the distillation of the generated water.

The imide oligomer obtained in step 1 preferably has an imine repeating structural unit formed by the compound providing the structural unit (A1) and the compound providing the structural unit (B1). By the above method, a solution containing the imide oligomer dissolved in the solvent can be obtained. The solution containing the imide oligomer obtained in the step 1 may contain at least a part of the components used as the tetracarboxylic acid component and the diamine component in the step 1 as long as the effect of the present invention is not impaired. as unreacted monomer.

[Step 2] In the step 2 of the production method of the present invention, the imine oligomer obtained in the step 1 is reacted with the tetracarboxylic acid component and the diamine component constituting the imide moiety to obtain an imine-imine acid Copolymer step.

The tetracarboxylic acid component used in the step 2 preferably contains the compound providing the structural unit (A1), and the entire amount thereof is preferably used in the step 1, and may contain a tetracarboxylic acid component other than the compound providing the structural unit (A1). The tetracarboxylic acid component other than the compound that provides the structural unit (A1) is preferably the compound that provides the structural unit (A2) or the compound that provides the structural unit (A3). The diamine component used in Step 2 preferably contains a compound that provides the structural unit (B1), and may contain diamine components other than the compound that provides the structural unit (B1) within a range that does not impair the effects of the present invention. The tetracarboxylic acid component other than the compound that provides the structural unit (B1) is preferably the compound that provides the structural unit (B2). In addition, when the polymer (X) (polyamic acid) substantially composed of the repeating unit represented by the formula (2) is obtained by carrying out only the step 2, the diamine component with respect to the tetracarboxylic acid component is preferably Set to 0.9 to 1.1 moles.

In Step 2, the method of reacting the tetracarboxylic acid component and the diamine component with the imide oligomer obtained in Step 1 is not particularly limited, and a known method can be used. The specific reaction method can be exemplified by (1) loading the imide oligomer, tetracarboxylic acid component, diamine component and solvent obtained in step 1 into the reactor, at 0～120°C, preferably at 5～120°C The method of stirring in the range of 80°C for 1 to 72 hours, (2) The imide oligomer obtained in step 1 and the solvent are charged into the reactor and dissolved, then the tetracarboxylic acid component and the diamine component are charged, and the 0 to 120°C, preferably a method of stirring in the range of 5 to 80°C for 1 to 72 hours. When the reaction is carried out at 80°C or lower, the molecular weight of the copolymer obtained in step 2 does not vary depending on the temperature history during polymerization, and furthermore, the progress of thermal imidization can be suppressed, and the copolymer can be produced stably thing.

By the above-mentioned method, the copolymer solution containing the amide-imide copolymer dissolved in the solvent can be obtained. In addition, by performing only step 1, a polyimide solution containing polyimide can be obtained, and by performing only step 2, a polyimide solution containing polyimide can be obtained. The concentration of the copolymer in the obtained solution is generally 1 to 50 mass %, preferably 3 to 35 mass %, preferably 5 to 30 mass %. In addition, the polyimide concentration in the obtained solution is generally 1 to 50% by mass, preferably 3 to 35% by mass, and preferably in the range of 5 to 30% by mass. In addition, the concentration of the polyamic acid in the obtained solution is generally 1 to 50% by mass, preferably 3 to 35% by mass, and preferably in the range of 5 to 30% by mass.

The number-average molecular weight of the imide-imide copolymer obtained by the above production method is preferably 5,000 to 500,000 from the viewpoint of the mechanical strength of the obtained polyimide film. In addition, from the same viewpoint, the weight average molecular weight (Mw) is preferably 10,000 to 800,000, and more preferably 100,000 to 300,000. In addition, the number-average molecular weight and the weight-average molecular weight of the copolymer can be obtained, for example, from standard polymethacrylate (PMMA) conversion values obtained by measuring by gel filtration chromatography. The number average molecular weight of the polyimide obtained by the above production method is preferably 5,000 to 500,000 from the viewpoint of the mechanical strength of the obtained polyimide film. In addition, from the same viewpoint, the weight average molecular weight (Mw) is preferably 10,000 to 800,000, and more preferably 100,000 to 300,000. The number-average molecular weight of the polyimide obtained by the above production method is preferably 5,000 to 500,000 from the viewpoint of the mechanical strength of the obtained polyimide film. In addition, from the same viewpoint, the weight average molecular weight (Mw) is preferably 10,000 to 800,000, and more preferably 100,000 to 300,000. Next, the raw materials and the like used in the present production method will be described.

[Tetracarboxylic acid component] As the tetracarboxylic acid component used as a raw material in the present production method, the compound represented by the formula (a1) can be exemplified as a compound that provides the structural unit (A1), but it is not limited to this, and in the case of providing the same structural unit It can also be its derivatives within the scope. Examples of the derivatives include tetracarboxylic acids corresponding to the compound represented by formula (a1) and alkyl esters of the tetracarboxylic acids. The compound providing the structural unit (A1) is preferably a compound represented by the formula (a1). Similarly, the compound that provides the structural unit (A2) can be exemplified by the compound represented by the formula (a2), but it is not limited thereto, and its derivatives can also be obtained within the scope of providing the same structural unit. Examples of the derivatives include tetracarboxylic acids corresponding to the compound represented by formula (a2) and alkyl esters of the tetracarboxylic acids. The compound providing the structural unit (A2) is preferably a compound represented by the formula (a2). In addition, the compound that provides the structural unit (A3) can be exemplified by the compound represented by the formula (a3), but it is not limited thereto, and a derivative thereof may also be provided within the scope of providing the same structural unit. The derivatives include tetracarboxylic acids corresponding to the compound represented by formula (a3) and alkyl esters of the tetracarboxylic acids. The compound providing the structural unit (A3) is preferably a compound represented by the formula (a3).

[Diamine component] The diamine component used as a raw material in the present production method includes diamine as a compound that provides the structural unit (B1), but it is not limited thereto, and may be the same as long as the same structural unit is provided. derivative. Examples of the derivatives include diisocyanates corresponding to diamines. The compound providing the structural unit (B1) is preferably a diamine. Likewise, the compound providing the structural unit (B2) can be exemplified by diamine, but it is not limited thereto, and a derivative thereof can also be provided within the scope of providing the same structural unit. Examples of the derivatives include diisocyanates corresponding to diamines. The compound providing the structural unit (B2) is preferably a diamine.

In the present invention, the feed ratio of the tetracarboxylic acid component and the diamine component used in all the steps of the production of the copolymer including the step 1 and the step 2 is preferably 1 mol of the tetracarboxylic acid component, two The amine component is 0.9 to 1.1 moles.

[Capping agent] Moreover, in the manufacture of the polymer (X), in addition to the above-mentioned tetracarboxylic acid component and diamine component, a terminal blocking agent may be used. When performing both steps 1 and 2, a capping agent is preferably used in step 2. The end-capping agent is preferably a monoamine or a dicarboxylic acid. The feed amount of the introduced end-capping agent is preferably 0.0001-0.1 mol, particularly preferably 0.001-0.06 mol, relative to 1 mol of the tetracarboxylic acid component. Monoamine end-capping agents, such as methylamine, ethylamine, propylamine, butylamine, benzylamine, 4-methylbenzylamine, 4-ethylbenzylamine, 4-dodecylbenzylamine, 3- Methylbenzylamine, 3-ethylbenzylamine, aniline, 3-methylaniline, 4-methylaniline, etc. Among these, benzylamine and aniline can be suitably used. The dicarboxylic acid type end-capping agent is preferably a dicarboxylic acid type, and a part thereof may be ring-closed. Recommended such as phthalic acid, phthalic anhydride, 4-chlorophthalic acid, tetrafluorophthalic acid, 2,3-diphenylketonedicarboxylic acid, 3,4-diphenylketonedicarboxylic acid acid, cyclopentane-1,2-dicarboxylic acid, 4-cyclohexene-1,2-dicarboxylic acid, etc. Among these, phthalic acid and phthalic anhydride can be suitably used.

[Solvent] The solvent used in the production method of the polymer (X) may be any solvent as long as it can dissolve the produced imide-amylic acid copolymer. For example, an aprotic solvent, a phenol type solvent, an ether type solvent, a carbonate type solvent, etc. are mentioned.

Specific examples of the aprotic solvent include N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, and N-methylcaprolactone. Amines, amide-based solvents such as 1,3-dimethylimidazolidinone, and tetramethylurea, lactone-based solvents such as γ-butyrolactone and γ-valerolactone, hexamethylphosphoric acid amide, hexamethyl phosphate Phosphorus-containing amide-based solvents such as phosphine triamide, sulfur-containing solvents such as dimethyl sulfoxide, dimethyl sulfoxide, and cyclobutane, ketone-based solvents such as acetone, butanone, cyclohexanone, and methylcyclohexanone Solvents, ester solvents such as acetic acid (2-methoxy-1-methylethyl), and the like.

Specific examples of the phenolic solvent include phenol, o-cresol, m-cresol, p-cresol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol -Xylenol, 3,4-Xylenol, 3,5-Xylenol, etc. Specific examples of ether-based 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 the carbonate-based solvent include ethyl carbonate, methylethyl carbonate, ethylidene carbonate, propylene carbonate, and the like. Among the above-mentioned reaction solvents, an amide-based solvent or a lactone-based solvent is preferred, an amide-based solvent is more preferred, and N-methyl-2-pyrrolidone is more preferred. The above-mentioned reaction solvents can be used alone or in combination of two or more.

(式(3)中，R ³為選自於由碳數1～30之烷基、苯基、烷氧基、丙烯醯基、甲基丙烯醯基、丙烯醯氧乙基、及甲基丙烯醯氧乙基構成之群組中之至少一種，n為0～2。) 藉由含有化合物(Y)，能夠得到具有耐熱性並且低黃色度之薄膜，並且可改善薄膜之透明性。 <Compound (Y)> The compound (Y) contained in the polymer composition of the present invention is represented by the following general formula (3). [Chemical 14]

(In formula (3), R ³ is selected from the group consisting of an alkyl group having 1 to 30 carbon atoms, a phenyl group, an alkoxy group, an acryl group, a methacryloyl group, an acryloxyethyl group, and a methacryloyl group. At least one of the group consisting of acyloxyethyl groups, and n is 0 to 2.) By containing the compound (Y), a film with heat resistance and low yellowness can be obtained, and the transparency of the film can be improved.

In formula (3), R ³ is selected from the group consisting of an alkyl group having 1 to 30 carbon atoms, a phenyl group, an alkoxy group, an acryl group, a methacryloyl group, an acryloxyethyl group, and a methacryloyl group At least one of the group consisting of oxyethyl groups is preferably an alkyl group having 1 to 30 carbon atoms. The majority of R ^{3 s} may be the same or different, preferably the same. n is 0-2, preferably 1-2.

The compound (Y) is a phosphorus compound, and a specific example of the compound (Y) may be at least one selected from the group consisting of an acidic phosphoric acid ester and phosphoric acid, and it is preferably an acidic phosphoric acid ester. Acidic phosphoric acid esters include isotridecyl acid phosphate, dibutyl phosphate, etc., preferably isotridecyl acid phosphate.

The content of the compound (Y) with respect to the polymer (X) is preferably 10 ppm or more and 10,000 ppm or less, more preferably 100 ppm or more and 5,000 ppm or less, and more preferably 500 ppm or more and 2,000 ppm or less. When the amount of the compound (Y) is within this range, a film having heat resistance and low yellowness can be obtained, and the transparency of the film can be improved. In addition, in this specification, "ppm" means mass parts per million.

[Varnish] The varnish of the present invention is formed by dissolving the above-mentioned polymer composition in an organic solvent. That is, the varnish of the present invention is formed by dissolving the polymer (X) and the compound (Y) in an organic solvent, and the varnish of the present invention contains the polymer (X), the compound (Y) and the organic solvent, and the polymer ( X) and compound (Y) are dissolved in the organic solvent. The organic solvent is not particularly limited as long as it can dissolve the polymer (X) and the compound (Y). The solvent used in the production of the polymer (X) is preferably used alone or in combination of two or more of the above-mentioned compounds. . The varnish of the present invention may be a compound (Y) mixed and dissolved in the above-mentioned polymer (X) solution, or may be further added with a diluting solvent.

When the polymer (X) contained in the varnish of the present invention contains the repeating unit (aramidic acid moiety) represented by the formula (2), from the viewpoint of efficient imidization of the aramidic acid moiety , can also contain imidization catalyst and dehydration catalyst. The imidization catalyst may be any imidization catalyst having a boiling point of 40°C or higher and 180°C or lower, and suitable examples include amine compounds having a boiling point of 180°C or lower. If the imidization catalyst has a boiling point of 180° C. or lower, there is no possibility that the film will be stained and the appearance will be damaged when the film is formed and dried at a high temperature. In addition, if the boiling point is an imidization catalyst of 40° C. or higher, the possibility of volatilization before sufficient imidization can be avoided. As an amine compound suitable for use as the imidization catalyst, pyridine or picoline can be exemplified. The above-mentioned imidization catalysts may be used alone or in combination of two or more. Examples of the dehydration catalyst include acid anhydrides such as acetic anhydride, propionic anhydride, n-butyric anhydride, benzoic anhydride, and trifluoroacetic anhydride; and carbodiimide compounds such as dicyclohexylcarbodiimide. These can also be used individually or in combination of 2 or more types.

Since the polymer (X) contained in the varnish of the present invention has solvent solubility, it can be used as a high-concentration varnish. The varnish of the present invention preferably contains the polymer (X) in an amount of 3 to 40% by mass, more preferably 5 to 40% by mass, and more preferably 10 to 30% by mass. The viscosity of the varnish should be 0.1～100Pa·s, preferably 0.1～20Pa·s. The viscosity of the varnish is the value measured at 25°C using an E-type viscometer. In addition, the varnish of the present invention may also contain inorganic fillers, adhesion promoters, release agents, flame retardants, UV stabilizers, surfactants, modifiers within the scope of not impairing the required properties of the polyimide film. Various additives such as leveling agent, defoaming agent, optical brightener, cross-linking agent, polymerization initiator, sensitizer, etc. The manufacturing method of the varnish of this invention is not specifically limited, A well-known method can be applied.

[Polyimide film and method for producing polyimide film] In the polyimide film of the present invention, when the polymer (X) contains the repeating unit (the amide moiety) represented by the formula (2), the amide film of the polymer (X) may contain the amide imide portion of the polymer (X). The resulting polyimide resin and compound (Y). In addition, when the polymer (X) is a polyimide, the polyimide, or a polyimide resin whose molecular weight is adjusted by further heating, and the compound (Y) are contained. Therefore, the polyimide film of the present invention is excellent in heat resistance and low in yellowness. The polyimide film of the present invention can be produced using the above-mentioned varnish.

The method for producing a polyimide film using the varnish of the present invention is not particularly limited, and the following method is suitable. That is, it is suitable to coat the above-mentioned varnish on the support and heat the method, specifically, it is suitable to dissolve the polymer (X) and the compound (Y) in the organic solvent and form the varnish and coat on the support and heat method. In addition, the polyimide film of the present invention is preferably a polyimide film obtained by coating the above-mentioned varnish on a support and heating, and specifically, it is preferable to dissolve the polymer (X) and the compound (Y) A varnish formed in an organic solvent is coated on a support and heated to obtain a polyimide film.

As a support, a smooth glass plate, a metal plate, a plastic, etc. are mentioned, for example. After the varnish is coated on the support, or formed into a film, the organic solvents such as the reaction solvent and the dilution solvent contained in the varnish are removed by heating to obtain a polymer film. When it has an imidic acid moiety, it is heated to imidize (dehydration ring closure) and then peeled off from the support, whereby a polyimide film can be produced. The weight-average molecular weight (Mw) of the polyimide resin contained in the polyimide film of the present invention is preferably 10,000 to 800,000, preferably 30,000 to 500,000, and more preferably 30,000 to 500,000 from the viewpoint of the mechanical strength of the film. 50,000-400,000 is more preferable, and 100,000-300,000 is still more preferable. In addition, the weight average molecular weight of this copolymer can be calculated|required by the standard polymethacrylate (PMMA) conversion value obtained by gel filtration chromatography, for example.

The heating temperature when the varnish of the present invention is dried to obtain a polymer film is preferably 50 to 150°C. The heating temperature when the polymer is imidized by heating is preferably 200 to 500°C, more preferably 250 to 450°C, and more preferably 300 to 400°C. In addition, the heating time is generally 1 minute to 6 hours, preferably 5 minutes to 2 hours, and more preferably 15 minutes to 1 hour. Heating gas environment, such as air, nitrogen, oxygen, hydrogen, nitrogen/hydrogen mixed gas, etc., in order to suppress the dyeing of the obtained polyimide resin, preferably nitrogen with an oxygen concentration of 100 ppm or less, and a hydrogen concentration of 0.5% or less. Nitrogen/hydrogen gas mixture. In addition, the method of imidization 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 according to the application, etc., preferably 1-250 μm, preferably 5-100 μm, more preferably 5-50 μm. With a thickness of 1 to 250 μm, practical use as a self-supporting film becomes possible. The thickness of the polyimide film can be easily adjusted by adjusting the solid content concentration and viscosity of the varnish.

By using the polymer composition of the present invention, a polyimide film having excellent heat resistance and low yellowness can be obtained, and the obtained polyimide film of the present invention has excellent heat resistance and low yellowness. Suitable physical property values of the film are as follows. For the total light transmittance, when a film with a thickness of 10 μm is made, it is preferably 85% or more, preferably 87% or more, and more preferably 89% or more. The yellowness (YI) is preferably 12 or less, more preferably 11 or less, and preferably 9 or less, more preferably 8 or less, from the viewpoint of being excellent in colorless property when it is made into a thin film with a thickness of 10 μm. In addition, the 1% weight reduction temperature is preferably 430°C or higher, more preferably 480°C or higher, more preferably 500°C or higher, and even more preferably 510°C or higher. Here, the 1% weight reduction temperature is the temperature at which the polyimide film is heated to 40-550°C at a heating rate of 10°C/min, and the weight is reduced by 1% compared to the weight at 300°C. In addition, the above-mentioned physical property values in the present invention can be specifically measured by the methods described in the Examples.

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

The present invention will be specifically described below by way of examples. However, the present invention is not limited to these examples. The 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 micrometer manufactured by Mitutoyo Co., Ltd. In addition, the film thicknesses of Example 5 and Comparative Example 6 were measured using a film thickness measuring device Filmetrics F20 (manufactured by Filmetrics Co., Ltd.).

(2) Total light transmittance, yellowness (YI) The total light transmittance was measured in accordance with JIS K7105:1981, and the YI was measured in accordance with ASTM D1925 (C light source, 2°), using a color turbidity simultaneous measuring device "COH7700" manufactured by Nippon Denshoku Industries Co., Ltd.

(3) 1% weight reduction temperature (Td1%) A differential thermogravimetric simultaneous measuring apparatus "NEXTA STA200RV" manufactured by Hitachi High-Tech Science Co., Ltd. was used. The sample was heated to 40 to 150°C at a temperature increase rate of 10°C/min, maintained at 150°C for 30 minutes, and was heated to 550°C after removing moisture. The temperature at which the weight was reduced by 1% compared with the weight after maintaining at 150° C. for 30 minutes was taken as the 1% weight loss temperature. The larger the weight reduction temperature value, the better.

The tetracarboxylic acid component and the diamine component used in Examples and Comparative Examples, as well as their abbreviations, are as follows. <Tetracarboxylic acid component> CpODA: norbornane-2-spiro-α-cyclopentanone-α'-spiro-2''-norbornane-5,5'',6,6''-tetracarboxylic acid Dianhydride (compound represented by formula (a1)) s-BPDA: 3,3',4,4'-biphenyltetracarboxylic dianhydride (manufactured by Mitsubishi Chemical Co., Ltd., compound represented by formula (a2s)) BPAF: 9,9-bis(3,4-dicarboxyphenyl)perylene anhydride (manufactured by JFE Chemical Co., Ltd.; compound represented by formula (a3)) <diamine component> 6FODA: 2,2'-bis(trifluoro) Methyl)-4,4'-diaminediphenyl ether (compound represented by formula (b11)) 4-BAAB: 4-aminophenyl-4-aminobenzoic acid (manufactured by Junyang Pharmaceutical Co., Ltd.; formula Compound represented by (b2) <Phosphorus compound> JP-513: Isotridecyl acid phosphate (manufactured by Johoku Chemical Industry Co., Ltd., in formula (3), R ³ is isotridecyl, and n is 1 The compound, and R ³ is isotridecyl, n is 2 compounds of 1: 1 mixture) DBP: dibutyl phosphate (Chengbei Chemical Industry Co., Ltd., in formula (3), R ³ is butyl base, n is 2 compound) phosphoric acid: in formula (3), n is 0 compound Trimethyl phosphate: in formula (3), R ³ is methyl, n is 3 compound Triphenylphosphine: In formula (3), R ³ is a phenyl group, and n is a compound of 3 <Other compounds> Irganox 1010 (antioxidant): neopentaerythritol tetra[3-(3,5-di-tert-butyl-4 -Hydroxybenzene) propionate] (manufactured by BASF JAPAN Co., Ltd.) <Surface conditioner> BYK-378: Silicone resin-based surface conditioner (manufactured by BYK-Chemie Japan Co., Ltd.)

Abbreviations and the like of solvents and catalysts used in Examples and Comparative Examples are as follows. NMP: N-methyl-2-pyrrolidone (manufactured by Tokyo Pure Chemical Industries, Ltd.) TEA: Triethylamine (manufactured by Kanto Chemical Co., Ltd.)

<Example 1> 26.899 g (0.0800 mol) were put into a 500 mL 5-neck round-bottomed flask equipped with a half-moon-shaped stirring blade made of stainless steel, a nitrogen introduction tube, a Dean-Stark apparatus equipped with a cooling tube, a thermometer, and a glass end cap. 6FODA and 94.146 g of NMP were stirred at a temperature of 50° C. in the system under a nitrogen atmosphere at a rotation speed of 200 rpm to obtain a solution. To this solution, 23.536 g (0.0800 mol) of s-BPDA and 23.536 g of NMP were put in at one time, and the mixture was directly stirred for 5 hours while maintaining at 50°C with a mantle heater. Then, after adding 84.059 g of NMP to make it homogenized, it returned to room temperature to obtain a polyamide varnish having a solid content concentration of 20% by mass. To 100 g of the obtained varnish, 0.02 g of JP-513 (1000 ppm relative to the polyamic acid) and 0.02 g of BYK-378 (1000 ppm relative to the polyamic acid) were added and stirred for 30 minutes to homogenize to obtain Polyamide composition varnish. Then, the obtained polyamide composition varnish was coated on a glass plate by spin coating, maintained at 80°C for 20 minutes on a hot plate, then moved to a hot air dryer, and heated at a rate of 5°C in a nitrogen atmosphere. The temperature was raised to 420° C./min, and heated at 420° C. for 60 minutes in a hot air dryer under a nitrogen atmosphere to evaporate the solvent and imidize it to obtain a polyimide film. The results are shown in Table 1.

<Examples 2, 3 and Comparative Examples 2 to 4> In addition to using 0.02 g of the phosphorus compound shown in Table 1 or other compounds (1000 ppm relative to the polyamic acid) in place of 0.02 g of JP-513 (1000 ppm relative to the polyamic acid), the In the same manner as in Example 1, a polyimide film was obtained. The results are shown in Table 1.

<Comparative Example 1> A polyimide film was obtained in the same manner as in Example 1 except that JP-513 was not used. The results are shown in Table 1.

<Example 4> Using 0.0800 mol of CpODA instead of 23.536 g (0.0800 mol) of s-BPDA, the maintenance temperature was set to 10° C. and stirred for 5 hours after the raw materials were put in at one time, except that the same method as in Example 1 was used. , to obtain a polyamide composition varnish. Next, the obtained polyimide composition varnish was coated on a glass plate by spin coating, maintained at 80°C for 20 minutes on a hot plate, then moved to a hot air dryer, and heated at a rate of 5°C/ The temperature was raised to 420 °C for 1 min, and heated at 420 °C for 60 minutes in a hot air dryer under a nitrogen atmosphere to evaporate the solvent to obtain a polyimide film. The results are shown in Table 1.

<Comparative Example 5> A polyimide film was obtained in the same manner as in Example 4 except that JP-513 was not used. The results are shown in Table 1.

<Example 5> Put 10.087 g (0.030 moles) into a 500 mL 5-neck round-bottomed flask equipped with a half-moon-shaped stirring blade made of stainless steel, a nitrogen introduction tube, a Dean-Stark apparatus equipped with a cooling tube, a thermometer, and a glass end cap. 6FODA and 47.017 g of NMP were stirred at a temperature of 70° C. in the system and a nitrogen atmosphere at a rotational speed of 200 rpm to obtain a solution. In this solution, 9.169 g (0.020 mol) of BPAF and 11.754 g of NMP were added at one time, and then 0.101 g of TEA was added as an imidization catalyst, and heated with a heating pack, which took about 20 minutes to make The temperature in the reaction system was raised to 190°C. The components distilled off were collected, and while the rotational speed was adjusted according to the increase in viscosity, the temperature in the reaction system was maintained at 190° C. and refluxed for 1 hour. Then, 147.043 g of NMP was added, and the temperature in the reaction system was cooled to 50° C. to obtain a solution containing an oligomer having a repeating structural unit of imide. To the obtained solution, 23.538 g (0.080 mol) of s-BPDA, 15.978 g (0.070 mol) of 4-BAAB, and 26.386 g of NMP were added in one portion, and the mixture was stirred at 50°C for 5 hours. Then, by adding NMP so that the solid content concentration might be about 15 mass %, it was made to be uniform, and the varnish (imide-imine-acid) containing the copolymer having the repeating structural unit of imide and the structural unit of imide was obtained. Copolymer varnishes). To 100 g of the obtained varnish, 0.015 g (1000 ppm relative to the imide-amyric acid copolymer) of JP-513 and 0.015 g (1000 ppm relative to the imide- imine acid copolymer) of BYK- 378, stirred for 30 minutes to make it homogenized to obtain a varnish of the imide-amylic acid copolymer composition. Next, the obtained amide-imide copolymer composition varnish was coated on a glass plate by spin coating, maintained at 80° C. for 20 minutes on a hot plate, and then moved to a hot-air dryer, under a nitrogen atmosphere, with The temperature was increased to 430°C at a heating rate of 5°C/min, and heated at 430°C in a hot air dryer for 60 minutes in a nitrogen atmosphere to evaporate the solvent and thermal imidization to obtain a polyimide film. The results are shown in Table 1.

<Comparative Example 6> A polyimide film was obtained by the same method as in Example 5 except that JP-513 was not used. The results are shown in Table 1. In addition, since the polyimide film obtained in Comparative Example 6 could not be peeled off from the glass plate, the total light transmittance and yellowness (YI) of Example 5 and Comparative Example 6 were measured including the glass plate. In addition, about the polyimide film obtained in Comparative Example 6, the 1% weight reduction temperature (Td1%) was not measured.

[Table 1]

As shown in Table 1, the polyimide film obtained from the polymer composition of the present invention was found to be excellent in heat resistance and low in yellowness. Furthermore, the polyimide film obtained from the polymer composition of the present invention is also excellent in transparency.

Claims (7)

A polymer composition comprising: a polymer (X) containing at least one selected from the group consisting of a repeating unit represented by the following general formula (1) and a repeating unit represented by the following general formula (2) , and the compound (Y) represented by the following general formula (3);

In formula (1), X ¹ is a tetravalent group having an alicyclic structure or an aromatic ring; In formula (2), X ² is a tetravalent group having an alicyclic structure or an aromatic ring, R ¹ and R ² are each independently hydrogen, an alkyl group having 1 to 6 carbon atoms, or an alkylsilyl group having 3 to 9 carbon atoms; in formula (3), R ³ is selected from the group consisting of an alkyl group having 1 to 30 carbon atoms, At least one of the group consisting of phenyl, alkoxy, acryl, methacryloyl, acryloxyethyl, and methacryloyloxyethyl, and n is 0-2. The polymer composition of claim 1, wherein the repeating unit represented by the formula (1) is 10 mol% or more relative to the total repeating unit of the polymer (X). The polymer composition of claim 1 or 2, wherein the repeating unit represented by the formula (2) is 10 mol% or more relative to the total repeating unit of the polymer (X). The polymer composition according to any one of claims 1 to 3, wherein the content of the compound (Y) is 10 ppm or more and 10,000 ppm or less with respect to the polymer (X). A varnish formed by dissolving the polymer composition of any one of claims 1 to 4 in an organic solvent. A polyimide film is obtained by coating the varnish according to claim 5 on a support and heating. A method for manufacturing a polyimide film, comprising coating the varnish as claimed in item 5 on a support and heating.