KR102422464B1 - Polyimide precursors, polyimides, polyimide films, varnishes and substrates - Google Patents

Abstract

(식 중, A₂는 방향족환 또는 지환 구조를 갖는 4가의 기이고, B₂는 방향족환 또는 지환 구조를 갖는 2가의 기이다. 단, 각 반복 단위에 포함되는 A₂ 및 B₂는 동일하거나 달라도 된다.)a repeating unit represented by the following general formula (5), wherein A ₂ in the general formula (5) contains a tetravalent group represented by the formula (A-1), and B ₂ in the general formula (5) There is provided a polyimide containing a divalent group represented by the formula (B-1), and A ₂ and/or B ₂ containing a tetravalent or divalent group containing a specific structure in a specific ratio. This polyimide has high transparency and a low coefficient of linear thermal expansion, and the thickness direction retardation (retardation) is also small.

(Wherein, A ₂ is a tetravalent group having an aromatic ring or alicyclic structure, and B ₂ is a divalent group having an aromatic ring or alicyclic structure. However, A ₂ and B ₂ included in each repeating unit are the same or It may be different.)

Description

Polyimide precursors, polyimides, polyimide films, varnishes and substrates

The present invention relates to a polyimide having high transparency, a low coefficient of linear thermal expansion, and a small thickness direction retardation (retardation), and a precursor thereof. The present invention also relates to varnishes and substrates comprising polyimide films, polyimide precursors or polyimides.

In recent years, development of optical materials, such as a liquid crystal aligning film and the protective film for color filters, in the field of display devices, such as an optical fiber and an optical waveguide in the field of optical communication, is advancing with the advent of the advanced information society. In particular, in the field|area of a display apparatus, examination of the plastic substrate which is lightweight and excellent in flexibility as a replacement for a glass substrate is performed, and development of the display which can bend or round is performed actively. For this reason, the optical material of higher performance which can be used for such a use is calculated|required.

The aromatic polyimide is essentially colored in yellowish brown due to intramolecular conjugation or formation of a charge transfer complex. For this reason, as a means of suppressing coloration, for example, by introducing a fluorine atom into the molecule, imparting flexibility to the main chain, introducing a bulky group as a side chain, etc., the formation of an intramolecular conjugate or charge transfer complex is inhibited, , a method of expressing transparency has been proposed.

Moreover, the method of expressing transparency by using a semi-cyclic or all-cyclic polyimide which does not in principle form a charge transfer complex is also proposed. In particular, a highly transparent semicyclic polyimide using aromatic tetracarboxylic dianhydride as the tetracarboxylic acid component and alicyclic diamine as the diamine component, and alicyclic tetracarboxylic dianhydride and diamine component as the tetracarboxylic acid component As such, many highly transparent semicyclic polyimides using aromatic diamine have been proposed.

For example, in Patent Document 1, as a tetracarboxylic acid component, norbornane-2-spiro-α-cyclopentanone-α′-spiro-2″-norbornane-5,5″,6,6 "-Tetracarboxylic dianhydride (abbreviation: CpODA) is used, and as a diamine component, 2,2'-bis(trifluoromethyl)benzidine (abbreviation: TFMB) or TFMB and other aromatic diamines (eg For example, a polyimide using TFMB:4,4'-diaminobenzanilide:9,9-bis(4-aminophenyl)fluorene = 5:4:1 (molar ratio)) is disclosed. CpODA having a specific stereoisomer ratio is used as the tetracarboxylic acid component, TFMB as the diamine component, and other aromatic diamines (eg, TFMB:4,4'-diaminobenzanilide = 5) A polyimide using :5 (molar ratio), etc.) is disclosed.

Moreover, in patent document 3, it is a polyimide resin containing the structural unit A derived from tetracarboxylic dianhydride, and the structural unit B derived from a diamine compound, and the structural unit A is a structural unit derived from CpODA (A -1), at least any one of a structural unit (A-2) derived from pyromellitic dianhydride and a structural unit (A-3) derived from 1,2,4,5-cyclohexanetetracarboxylic dianhydride Structural unit B includes a structural unit (B-1) derived from 9,9-bis(4-aminophenyl)fluorene, and structural unit (B-1) in structural unit B including species A polyimide resin having a ratio of 60 mol% or more is disclosed. More specifically, in Example 4 of Patent Document 3, a polyimide resin is produced from CpODA (A-1) and 9,9-bis(4-aminophenyl)fluorene (B-1). In Example 5 of Patent Document 3, CpODA (A-1) and 1,2,4,5-cyclohexanetetracarboxylic dianhydride (A-3) and 9,9-bis(4-aminophenyl)flu A polyimide resin ((A-1):(A-3)=1:1 (molar ratio)) is produced from Orene (B-1). In Example 6 of Patent Document 3, polyimide is obtained from CpODA (A-1), 9,9-bis(4-aminophenyl)fluorene (B-1) and 2,2'-dimethylbenzidine (B-2). A resin ((B-1):(B-2)=4:1 (molar ratio)) is being prepared.

In Example 1 and Comparative Example 1 of Patent Document 4, CpODA, 4,4'-diamino-2,2'-dimethylbiphenyl and 9,9-bis(4-aminophenyl)fluorene (molar ratio: 1/1) and polyimides obtained from CpODA and 9,9-bis(4-aminophenyl)fluorene are described.

International Publication No. 2013/179727 International Publication No. 2014/046064 International Publication No. 2017/191822 Japanese Patent Laid-Open No. 2017-133027

Depending on the use, for example, in a display use etc., in addition to having high transparency and a low coefficient of linear thermal expansion, the polyimide and polyimide film with a small thickness direction retardation (retardation) are calculated|required. When light transmits through a film having a large retardation in the thickness direction, problems such that the color of the transmitted light is not accurately displayed, the color is spread, or the viewing angle is narrowed may occur. Therefore, in particular in a display use etc., it is desired to reduce the thickness direction phase difference.

An object of this invention is to provide the polyimide which has high transparency, a low coefficient of linear thermal expansion, and also small thickness direction retardation (retardation), and its precursor.

The present invention relates to each of the following clauses.

1. A polyimide precursor comprising a repeating unit represented by the following general formula (1),

2 A ₁ of the following general formula (1) contains a tetravalent group represented by the following formula (A-1), and B ₁ of the following general formula (1) is 2 represented by the following formula (B-1) including the flag of the family,

Further, A ₁ and/or B ₁ of the following general formula (1) contains a tetravalent or divalent group containing a structure represented by the following formula (2), or A ₁ of the following general formula (1) This includes a tetravalent group represented by the following formula (3) and/or a tetravalent group represented by the following formula (4),

A tetravalent group represented by the formula (A-1) in 100 mol% of A ₁ in the general formula (1), a tetravalent group containing a structure represented by the formula (2), a tetravalent group represented by the formula (3) , and the content ratio of the sum of the tetravalent groups represented by the formula (4), the divalent group represented by the formula (B-1) in 100 mol% of B ₁ in the general formula (1), and the formula (2) The sum of the content ratio of the sum of the divalent groups including the structure shown is 120 mol% or more,

However, the tetravalent group represented by Formula (A-1), the tetravalent group containing the structure represented by Formula (2), the tetravalent group represented by Formula (3), and 4 represented by Formula (4) The ratio of the tetravalent group including the structure represented by formula (2), the tetravalent group represented by the formula (3), and the tetravalent group represented by the formula (4) to the sum of the valent groups is 80 mol % or less, and

The ratio of the divalent group including the structure represented by the formula (2) to the sum of the divalent group represented by the formula (B-1) and the divalent group including the structure represented by the formula (2) is , Polyimide precursor, characterized in that 80 mol% or less.

(Wherein, A ₁ is a tetravalent group having an aromatic ring or an alicyclic structure, B ₁ is a divalent group having an aromatic ring or an alicyclic structure, and R ₁ and R ₂ are each independently hydrogen and having 1 to 6 carbon atoms. It is an alkyl group or an alkylsilyl group having 3 to 9 carbon atoms, provided that A ₁ and B ₁ included in each repeating unit may be the same or different.)

2. A polyimide comprising a repeating unit represented by the following general formula (5),

A ₂ of the following general formula (5) contains a tetravalent group represented by the following formula (A-1), and B ₂ of the following general formula (5) is 2 represented by the following formula (B-1) including the flag of the family,

Further, A ₂ and/or B ₂ of the following general formula (5) contains a tetravalent or divalent group containing a structure represented by the following formula (2), or A ₂ of the following general formula (5) contains a tetravalent group represented by the following formula (3) and/or a tetravalent group represented by the following formula (4);

A tetravalent group represented by the formula (A-1) in 100 mol% of A ₂ in the general formula (5), a tetravalent group containing a structure represented by the formula (2), a tetravalent group represented by the formula (3) , and the content ratio of the sum of the tetravalent groups represented by the formula (4), the divalent group represented by the formula (B-1) in 100 mol% of B ₂ in the general formula (5), and the formula (2) The sum of the content ratio of the sum of the divalent groups including the structure shown is 120 mol% or more,

However, the tetravalent group represented by Formula (A-1), the tetravalent group containing the structure represented by Formula (2), the tetravalent group represented by Formula (3), and 4 represented by Formula (4) The ratio of the tetravalent group including the structure represented by formula (2), the tetravalent group represented by the formula (3), and the tetravalent group represented by the formula (4) to the sum of the valent groups is 80 mol % or less, and

The ratio of the divalent group including the structure represented by the formula (2) to the sum of the divalent group represented by the formula (B-1) and the divalent group including the structure represented by the formula (2) is , Polyimide, characterized in that 80 mol% or less.

(Wherein, A ₂ is a tetravalent group having an aromatic ring or alicyclic structure, and B ₂ is a divalent group having an aromatic ring or alicyclic structure. However, A ₂ and B ₂ contained in each repeating unit are the same or different.)

3. The polyimide obtained from the polyimide precursor as described in said item|item 1.

4. A varnish containing the polyimide precursor according to the above item 1 or the polyimide according to the above item 2.

5. A polyimide film obtained by using the varnish containing the polyimide precursor according to the above item 1 or the polyimide according to the above item 2 .

6. The film containing the polyimide according to the above item 2 or 3 or the polyimide film according to the above item 5 is formed on a glass substrate, The laminate characterized in that.

7. A substrate for a display, a touch panel, or a solar cell comprising the polyimide according to the above item 2 or 3 or the polyimide film according to the above item 5.

ADVANTAGE OF THE INVENTION According to this invention, it has high transparency, a low coefficient of linear thermal expansion, and can provide the polyimide with a small thickness direction retardation (retardation), and its precursor.

Since the polyimide obtained from the polyimide precursor of the present invention and the polyimide of the present invention have high transparency, a low coefficient of linear thermal expansion, and a small thickness direction retardation (retardation), in order to form a substrate for display applications, etc. can be used appropriately. Moreover, the polyimide obtained from the polyimide precursor of this invention and the polyimide of this invention can be used suitably also in order to form the board|substrate for touch panels and solar cells.

The polyimide precursor of this invention is a polyimide precursor containing the repeating unit represented by the said General formula (1). The total content of the repeating units represented by the general formula (1) is preferably 90 mol% or more, more preferably 95 mol% or more, and particularly preferably 100 mol% with respect to all the repeating units. In General Formula (1), A ₁ is a tetravalent group having an aromatic ring or an alicyclic structure, and is preferably a tetravalent group having an alicyclic structure. In General Formula (1), B ₁ is a divalent group having an aromatic ring or an alicyclic structure, and is preferably a divalent group having an aromatic ring.

And in the polyimide precursor of this invention, A ₁ in the said General formula (1) contains the tetravalent group represented by the said Formula (A-1), Moreover, B ₁ in the said General formula (1) is said A tetravalent or divalent group containing a divalent group represented by the formula (B-1), and wherein A ₁ and/or B ₁ of the general formula (1) includes a structure represented by the formula (2) or A ₁ in the general formula (1) contains a tetravalent group represented by the formula (3) and/or a tetravalent group represented by the formula (4). A ₁ and/or B ₁ contains a tetravalent or divalent group containing a structure represented by the formula (2), and A ₁ is a tetravalent group represented by the formula (3) and/or the above The tetravalent group represented by Formula (4) may be included.

In addition, their content is a tetravalent group containing the structure represented by the tetravalent group represented by Formula (A- ₁ ), Formula (2), Formula (3) in 100 mol% of A1 of General formula (1) ) of the total content of the tetravalent group represented by the tetravalent group and the tetravalent group represented by the formula (4), and the divalent group represented by the formula (B-1) in 100 mol% of B ₁ in the general formula (1) and the sum of the content ratio of the sum of the divalent groups containing the structure represented by the formula (2) is 120 mol% or more, preferably 160 mol% or more, more preferably 180 mol% or more. . However, the tetravalent group represented by the tetravalent group represented by Formula (A- ₁ ) in A1 of General formula (1), the structure represented by Formula (2), the tetravalent group represented by Formula (3) With respect to the sum of the group and the tetravalent group represented by the formula (4), the tetravalent group containing the structure represented by the formula (2), the tetravalent group represented by the formula (3), and the formula (4) The ratio of the tetravalent group represented is 80 mol% or less, and the divalent group represented by the formula (B-1) in B ₁ of the general formula (1), and the structure represented by the formula (2) The ratio of the divalent group containing the structure represented by Formula (2) with respect to the sum total of the divalent group contained is 80 mol% or less. Moreover, it is preferable that the sum of these two ratios is 125 mol% or less.

The polyimide of this invention is a polyimide containing the repeating unit represented by the said General formula (5). The total content of the repeating units represented by the general formula (5) is preferably 90 mol% or more, more preferably 95 mol% or more, and particularly preferably 100 mol% with respect to all the repeating units. In general formula (5), A ₂ is a tetravalent group having an aromatic ring or an alicyclic structure, and is preferably a tetravalent group having an alicyclic structure. In general formula (5), B2 is a _divalent group which has an aromatic ring or an alicyclic structure, and it is preferable that it is a divalent group which has an aromatic ring.

And, in the polyimide of the present invention, A ₂ in the general formula (5) contains a tetravalent group represented by the formula (A-1), and in the general formula (5), B ₂ is the formula A divalent group represented by (B-1) is included, and A ₂ and/or B ₂ in the general formula (5) includes a tetravalent or divalent group including a structure represented by the formula (2). Alternatively, A ₂ in the general formula (5) contains a tetravalent group represented by the formula (3) and/or a tetravalent group represented by the formula (4). A ₂ and/or B ₂ contains a tetravalent or divalent group containing the structure represented by the formula (2), and A ₂ is a tetravalent group represented by the formula (3) and/or the above The tetravalent group represented by Formula (4) may be included.

In addition, their content is a tetravalent group containing the structure represented by the tetravalent group represented by Formula (A-1), Formula ( ₂ ) in 100 mol% of A2 of General formula (5), Formula (3) The content ratio of the total of the tetravalent group represented by the tetravalent group and the tetravalent group represented by the formula (4), and the divalent group represented by the formula (B-1) in 100 mol% of B ₂ in the general formula (5); And it is preferable that the sum of the content rate of the sum total of the divalent group containing the structure represented by Formula (2) is 120 mol% or more, Preferably it is 160 mol% or more, More preferably, it is 180 mol% or more. However, the tetravalent group represented by the tetravalent group represented by Formula (A _- 1) in A2 of General formula (5), the structure represented by Formula (2), the tetravalent group represented by Formula (3) With respect to the sum of the group and the tetravalent group represented by the formula (4), the tetravalent group containing the structure represented by the formula (2), the tetravalent group represented by the formula (3), and the formula (4) The ratio of the tetravalent group represented is 80 mol% or less, and the divalent group represented by the formula (B-1) in B ₂ of the general formula (5) and the structure represented by the formula (2) The ratio of the divalent group containing the structure represented by Formula (2) with respect to the sum total of the divalent group to contain is 80 mol% or less. Moreover, it is preferable that the sum of these two ratios is 125 mol% or less.

In this specification, the following abbreviations are used suitably.

CpODA: norbornane-2-spiro-α-cyclopentanone-α′-spiro-2″-norbornane-5,5″,6,6″-tetracarboxylic dianhydride

CpODA and the like: norbornane-2-spiro-α-cyclopentanone-α′-spiro-2″-norbornane-5,5″,6,6″-tetracarboxylic acids (tetracarboxylic acids, etc.) tetracarboxylic acid and tetracarboxylic acid derivatives such as tetracarboxylic acid dianhydride, tetracarboxylic acid silyl ester, tetracarboxylic acid ester, and tetracarboxylic acid chloride)

TFMB: 2,2'-bis(trifluoromethyl)benzidine

The tetracarboxylic-acid component which provides the tetravalent group represented by the said Formula (A-1) is CpODA etc., The diamine component which provides the bivalent group represented by the said Formula (B-1) is TFMB. A polyimide obtained from CpODA etc. TFMB, that is, A ₁ is a tetravalent group represented by the formula (A-1), and B ₁ is a divalent group represented by the formula (B-1). The polyimide obtained from a polyimide precursor containing a repeating unit and A ₂ are a tetravalent group represented by the formula (A-1), and B ₂ is a divalent group represented by the formula (B-1). (5) Although the polyimide containing this repeating unit has high transparency and a low coefficient of linear thermal expansion, it exists in the tendency for thickness direction retardation (retardation) to be comparatively large. When a polyimide film is used for a display application or the like, if the thickness direction retardation is large as described above, there may be problems in that the color of transmitted light is not displayed correctly, the color is spread, or the viewing angle is narrowed. On the other hand, in the said content (ratio), A1 of General formula ( ₁ ) which is a structure derived from a tetracarboxylic-acid component, A2 of General formula ( ₅ ), and/or General which is a structure derived from a diamine component A group containing the structure represented by the formula (2) is introduced into B ₁ of the formula (1) and B ₂ of the general formula (5), or a structure derived from a tetracarboxylic acid component of the general formula (1) By introducing the tetravalent group represented by the formula (3) and/or the tetravalent group represented by the formula (4) into A ₁ and A ₂ in the general formula (5), high transparency and low coefficient of linear thermal expansion are maintained. While doing so, the thickness direction retardation (retardation) can be reduced. As a result, it is possible to obtain a polyimide having high transparency and a low coefficient of linear thermal expansion, and also having a small thickness direction retardation (retardation).

Here, the structure represented by the said Formula (2) may be connected with the adjacent aromatic ring by a direct bond, an ether bond, etc., for example, the structure represented by following formula (2') may be sufficient as it.

(Wherein R is a direct bond or an ether bond (-O-).)

The aromatic ring contained in the structure represented by the formula (2) may be substituted with an alkyl group such as a methyl group, a fluorinated alkyl group such as a trifluoromethyl group, or a substituent such as a halogeno group, but usually those having no substituent desirable. In addition, the substitution position is not specifically limited.

The tetracarboxylic acid component which gives the tetravalent group containing the structure represented by the said Formula (2) is tetracarboxylic acid etc. containing the structure represented by the said Formula (2), For example, 9,9' -bis(3,4-dicarboxyphenyl)fluorene dianhydride and other derivatives (other than tetracarboxylic dianhydride such as tetracarboxylic acid silyl ester, tetracarboxylic acid ester, and tetracarboxylic acid chloride) tetracarboxylic acid derivative) and the like. The diamine component which gives the divalent group containing the structure represented by the said Formula (2) is a diamine containing the structure represented by the said Formula (2), For example, 9,9-bis (4-aminophenyl) Fluorene, 9,9-bis(4-amino-3-chlorophenyl)fluorene, 9,9-bis(4-amino-3-fluorophenyl)fluorene, 9,9-bis(4-amino- 3-methylphenyl)fluorene, 4,4'-(spiro[fluorene-9,9'-xanthene]-3',6'-diylbis(oxy))dianiline, etc. are mentioned.

In addition, the tetracarboxylic-acid component which gives the tetravalent group represented by said Formula (3) is 1,2,4,5- cyclohexane tetracarboxylic acid etc..

The tetracarboxylic acid component which provides the tetravalent group represented by said Formula (4) is 2,3,3',4'- biphenyltetracarboxylic acid etc.

In other words, the polyimide precursor of the present invention and the polyimide of the present invention are

(a-1) CpODA, etc.;

(a-2) 2,3,3',4'-ratio, such as tetracarboxylic acids containing a structure represented by said Formula (2), 1,2,4,5-cyclohexanetetracarboxylic acids, etc. Any one or more types, such as phenyltetracarboxylic acid

A tetracarboxylic acid component comprising:

(b) the diamine component containing TFMB or the diamine component containing TFMB and the diamine containing the structure represented by said Formula (2)

obtained from, or

or,

(a) a tetracarboxylic acid component comprising CpODA and the like;

(b) TFMB and the diamine component containing the diamine containing the structure represented by said Formula (2)

is obtained from

As CpODA of the tetracarboxylic acid component used herein, among six stereoisomers, trans-endo-endo-norbornane-2-spiro-α-cyclopentanone-α′-spiro-2″-nor Bornane-5,5",6,6"-tetracarboxylic acids, etc. (trans-endo-endo form) and/or cis-endo-endo-norbornane-2-spiro-α-cyclopentanone-α In some cases, it is preferable to include '-spiro-2"-norbornane-5,5",6,6"-tetracarboxylic acids (cis-endo-endo form). In a certain embodiment, the ratio of the trans-endo-endo body and/or the cis-endo-endo body in CpODA etc. in total is preferably 80 mol% or more, more preferably 90 mol% or more, and still more preferably It is preferably 95 mol% or more, particularly preferably 99 mol% or more.

As 1,2,4,5-cyclohexanetetracarboxylic acids etc. of the tetracarboxylic acid component used here, 1R,2S,4S,5R- cyclohexanetetracarboxylic acids etc. among 6 types of stereoisomers are used here. In some cases, it is desirable to include In a certain embodiment, the ratio of 1R,2S,4S,5R-cyclohexanetetracarboxylic acids in 1,2,4,5-cyclohexanetetracarboxylic acids etc. is preferably 50 mol% or more, more preferably It is preferably 80 mol% or more, more preferably 90 mol% or more, and particularly preferably 95 mol% or more.

CpODA etc. may be used individually by 1 type, and may be used in combination of multiple types. Further, tetracarboxylic acids having a structure represented by the formula (2), 1,2,4,5-cyclohexanetetracarboxylic acids, etc., and 2,3,3',4'-biphenyltetracarboxylic acids Acids etc. may be used individually by 1 type, and may be used in combination of multiple types. The diamine containing the structure represented by the said Formula (2) may be used individually by 1 type, and may also be used in combination of multiple types.

As another tetracarboxylic acid component which gives the repeating unit represented by the said General formula (1) or the repeating unit represented by the said General formula (5), any other aromatic or alicyclic tetracarboxylic acid can be used. Although not particularly limited, for example, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane, 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2, 3,4-tetrahydronaphthalene-1,2-dicarboxylic acid, pyromellitic acid, 3,3',4,4'-benzophenonetetracarboxylic acid, 3,3',4,4'-biphenyl tetracarboxylic acid, 4,4'-oxydiphthalic acid, bis(3,4-dicarboxyphenyl)sulfone dianhydride, m-terphenyl-3,4,3',4'-tetracarboxylic dianhydride, p-terphenyl-3,4,3',4'-tetracarboxylic dianhydride, biscarboxyphenyldimethylsilane, bisdicarboxyphenoxydiphenylsulfide, sulfonyldiphthalic acid, 1,2,3,4-cyclo Butanetetracarboxylic acid, isopropylidenediphenoxybisphthalic acid, [1,1'-ratio (cyclohexane)]-3,3',4,4'-tetracarboxylic acid, [1,1'-ratio (Cyclohexane)]-2,3,3',4'-tetracarboxylic acid, [1,1'-bi(cyclohexane)]-2,2',3,3'-tetracarboxylic acid, 4 ,4'-methylenebis(cyclohexane-1,2-dicarboxylic acid), 4,4'-(propane-2,2-diyl)bis(cyclohexane-1,2-dicarboxylic acid), 4 ,4'-oxybis(cyclohexane-1,2-dicarboxylic acid), 4,4'-thiobis(cyclohexane-1,2-dicarboxylic acid), 4,4'-sulfonylbis( Cyclohexane-1,2-dicarboxylic acid), 4,4′-(dimethylsilane diyl)bis(cyclohexane-1,2-dicarboxylic acid), 4,4′-(tetrafluoropropane-2 ,2-diyl)bis(cyclohexane-1,2-dicarboxylic acid), octahydropentalene-1,3,4,6-tetracarboxylic acid, bicyclo[2.2.1]heptane-2,3 ,5,6-tetracarboxylic acid, 6-(carboxymethyl)bicyclo[2.2.1]heptane-2,3,5-tricarboxylic acid, bicyclo[2.2.2]octane-2,3,5 ,6-Tetracarboxylic acid, bicyclo[2.2.2]oct-5-ene-2,3,7,8-tetracarboxylic acid, tricyclo[4.2.2.02,5]decane-3,4,7 ,8-tetracarboxylic acid, tricyclo[4.2.2.02,5]deca-7-ene-3,4,9,10-tetracarboxylic acid, 9-oxatricyclo[4.2.1.02,5]nonane- 3,4,7,8-Tetracarboxylic acid, (4arH,8acH)-decahydr Rho-1t,4t:5c,8c-dimethanonaphthalene-2c,3c,6c,7c-tetracarboxylic acid, (4arH,8acH)-decahydro-1t,4t:5c,8c-dimethanonaphthalene- 2t, 3t, 6c, 7c-tetracarboxylic acid, and these tetracarboxylic acid derivatives (tetracarboxylic dianhydride, etc.) etc. are mentioned. Among them, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane, 4,4'-oxydiphthalic acid, 1,2,3,4-cyclobutanetetracarboxylic acid, (4arH, 8acH)-decahydro-1t,4t:5c,8c-dimethanonaphthalene-2c,3c,6c,7c-tetracarboxylic acid, (4arH,8acH)-decahydro-1t,4t:5c,8c-di Derivatives, such as methanonaphthalene-2t,3t,6c,7c-tetracarboxylic acid, and these acid dianhydrides are more preferable. These tetracarboxylic-acid components may be used independently and can also be used in combination of multiple types.

Any of other aromatic or alicyclic diamine can be used as another diamine component which provides the repeating unit of the said General formula (1) or the repeating unit represented by the said General formula (5). Although not particularly limited, for example, p-phenylenediamine, m-phenylenediamine, benzidine, 3,3'-diamino-biphenyl, 3,3'-bis(trifluoromethyl)benzidine, m- Tollidine, 4,4'-diaminobenzanilide, 3,4'-diaminobenzanilide, N,N'-bis(4-aminophenyl)terephthalamide, N,N'-p-phenylenebis(p -aminobenzamide), 4-aminophenoxy-4-diaminobenzoate, bis(4-aminophenyl)terephthalate, biphenyl-4,4'-dicarboxylic acid bis(4-aminophenyl)ester; p-phenylenebis(p-aminobenzoate), bis(4-aminophenyl)-[1,1'-biphenyl]-4,4'-dicarboxylate, [1,1'-biphenyl] -4,4'-diylbis(4-aminobenzoate), 4,4'-oxydianiline, 3,4'-oxydianiline, 3,3'-oxydianiline, bis(4-aminophenyl) Sulfide, p-methylenebis(phenylenediamine), 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 1,4-bis(4-amino) Phenoxy) benzene, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis (4-aminophenyl) hexafluoropropane, bis (4-aminophenyl) Sulfone, 3,3-bis((aminophenoxy)phenyl)propane, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, bis(4-(4-aminophenoxy)di Phenyl) sulfone, bis (4- (3-aminophenoxy) diphenyl) sulfone, octafluorobenzidine, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 3,3'-dichloro- 4,4'-diaminobiphenyl, 3,3'-difluoro-4,4'-diaminobiphenyl, 4,4'-bis(4-aminophenoxy)biphenyl, 4,4'- Bis(3-aminophenoxy)biphenyl, 1,4-diaminocyclohexane, 1,4-diamino-2-methylcyclohexane, 1,4-diamino-2-ethylcyclohexane, 1,4- Diamino-2-n-propylcyclohexane, 1,4-diamino-2-isopropylcyclohexane, 1,4-diamino-2-n-butylcyclohexane, 1,4-diamino-2-iso Butylcyclohexane, 1,4-diamino-2-sec-butylcyclohexane, 1,4-diamino-2-tert-butylcyclohexane, 1,2-diaminocyclohexane, 1,4-diaminocycle Rohexane etc. and these derivatives are mentioned. Among these, p-phenylenediamine, m-tolidine, 4,4'-oxydianiline, 1,4-bis(4-aminophenoxy)benzene, 4,4'-bis(4-aminophenoxy) ) biphenyl etc. are more preferable. These diamine components may be used independently and can also be used in combination of multiple types.

The polyimide precursor of the present invention and the polyimide of the present invention contain at least one repeating unit other than the repeating unit represented by the general formula (1) or the repeating unit represented by the general formula (5) it may be It does not specifically limit as a tetracarboxylic-acid component and diamine component which provides another repeating unit, Both other well-known tetracarboxylic acid and well-known diamine can be used. In addition, when the diamine component to combine is not the diamine component which provides the repeating unit represented by the said General formula (1) or the repeating unit represented by the said General formula (5), the tetracarboxylic-acid component which provides another repeating unit Silver is exemplified as a tetracarboxylic acid component giving the repeating unit represented by the general formula (1) or the repeating unit represented by the general formula (5) (CpODA, etc., a structure represented by the formula (2) tetracarboxylic acids containing In addition, when the tetracarboxylic acid component to be combined is not the tetracarboxylic acid component which provides the repeating unit represented by the said General formula (1) or the repeating unit represented by the said General formula (5), another repeating unit is given The diamine component to be exemplified as a diamine component giving the repeating unit represented by the general formula (1) or the repeating unit represented by the general formula (5) (TFMB, the structure represented by the formula (2) containing diamine is also included).

In the polyimide precursor of the present invention, R ₁ and R ₂ in the general formula (1) are each independently hydrogen, an alkyl group having 1 to 6 carbon atoms, preferably an alkyl group having 1 to 3 carbon atoms (especially preferably a methyl group or an ethyl group) or an alkylsilyl group having 3 to 9 carbon atoms (especially preferably a trimethylsilyl group or a t-butyldimethylsilyl group). R ₁ , R ₂ can change the type of the functional group and the introduction rate of the functional group by the manufacturing method described later.

The introduction rate of the functional group is not particularly limited, but when an alkyl group or an alkylsilyl group is introduced, each of R ₁ and R ₂ is 25% or more, preferably 50% or more, more preferably 75% or more of an alkyl group or an alkyl group. It can be done in the silyl. When 25% or more of each of R ₁ and R ₂ is an alkyl group or an alkylsilyl group, the storage stability of the polyimide precursor is excellent.

The polyimide precursor of the present invention is each independently prepared by _{1) polyamic acid (R 1 and} R ₂ are hydrogen), ₂ ) polyamic acid ester (R ₁ , R At least a portion of ₂ is an alkyl group), 3) 4) polyamic acid silyl ester (R ₁ , R ₂ at least a part of which is an alkylsilyl group). And the polyimide precursor of this invention can be manufactured easily with the following manufacturing methods for every this classification|categorization. However, the manufacturing method of the polyimide precursor of this invention is not limited to the following manufacturing methods.

1) polyamic acid

The polyimide precursor of the present invention contains approximately equimolar amounts of tetracarboxylic dianhydride and diamine component as a tetracarboxylic acid component in a solvent, preferably, a molar ratio of the diamine component to the tetracarboxylic acid component [number of moles of diamine component/tetra The number of moles of the carboxylic acid component] is preferably 0.90 to 1.10, more preferably 0.95 to 1.05, for example, by reacting at a relatively low temperature of 120° C. or less while suppressing imidization, polyimide precursor solution composition can be obtained suitably as

Although the synthesis method of the polyimide precursor of this invention is not limited, More specifically, diamine is melt|dissolved in an organic solvent, tetracarboxylic dianhydride is gradually added to this solution, stirring, 0-120 degreeC , Preferably, a polyimide precursor is obtained by stirring in the range of 5-80 degreeC for 1-72 hours. Since the molecular weight of a polyimide precursor goes up easily, the order of addition of diamine and tetracarboxylic dianhydride in the said manufacturing method is preferable. Moreover, it is also possible to reverse the addition order of the diamine and tetracarboxylic dianhydride of the said manufacturing method, and it is preferable at the point which a precipitate reduces.

Moreover, when the molar ratio of a tetracarboxylic-acid component and a diamine component is an excess of a diamine component, if necessary, the carboxylic acid derivative of the quantity substantially equivalent to the excess number of moles of a diamine component is added, and a tetracarboxylic-acid component and a diamine component The molar ratio of can be made close to about equivalent. Examples of the carboxylic acid derivative herein include tetracarboxylic acid that does not substantially increase the viscosity of the polyimide precursor solution, that is, does not substantially participate in molecular chain extension, or tricarboxylic acid and anhydride thereof that function as a terminator. , dicarboxylic acids and their anhydrides are suitable.

2) polyamic acid ester

After reacting tetracarboxylic dianhydride with arbitrary alcohol to obtain diester dicarboxylic acid, it is made to react with a chlorinating reagent (thionyl chloride, oxalyl chloride, etc.) to obtain diester dicarboxylic acid chloride. A polyimide precursor is obtained by stirring this diester dicarboxylic acid chloride and diamine in -20-120 degreeC, Preferably it is -5-80 degreeC for 1-72 hours. Moreover, a polyimide precursor is obtained simply also by carrying out dehydration-condensation of diester dicarboxylic acid and diamine using a phosphorus type condensing agent, a carbodiimide condensing agent, etc.

Since the polyimide precursor obtained by this method is stable, it can also refine|purify, such as reprecipitation, by adding solvents, such as water and alcohol.

3) polyamic acid silyl ester (indirect method)

In advance, diamine and a silylating agent are made to react, and the silylated diamine is obtained. If necessary, the silylated diamine is purified by distillation or the like. Then, the silylated diamine is dissolved in the dehydrated solvent, and while stirring, tetracarboxylic dianhydride is gradually added, and stirred in the range of 0 to 120 ° C., preferably 5 to 80 ° C. for 1 to 72 hours. , a polyimide precursor is obtained.

As the silylating agent used herein, it is suitable to use a silylating agent that does not contain chlorine since it is not necessary to purify the silylated diamine. Examples of the chlorine atom-free silylating agent include N,O-bis(trimethylsilyl)trifluoroacetamide, N,O-bis(trimethylsilyl)acetamide, and hexamethyldisilazane. N,O-bis(trimethylsilyl)acetamide and hexamethyldisilazane are particularly preferable because they do not contain a fluorine atom and are low in cost.

In the silylation reaction of diamine, an amine catalyst such as pyridine, piperidine or triethylamine can be used in order to accelerate the reaction. This catalyst can be used as it is as a polymerization catalyst of a polyimide precursor.

4) Polyamic acid silyl ester (direct method)

A polyimide precursor is obtained by mixing the polyamic acid solution obtained by the method of 1) and a silylating agent, and stirring in 0-120 degreeC, Preferably it is 5-80 degreeC for 1-72 hours.

As the silylating agent used herein, it is preferable to use a chlorine-free silylating agent because it is not necessary to purify the silylated polyamic acid or the obtained polyimide. Examples of the chlorine atom-free silylating agent include N,O-bis(trimethylsilyl)trifluoroacetamide, N,O-bis(trimethylsilyl)acetamide, and hexamethyldisilazane. N,O-bis(trimethylsilyl)acetamide and hexamethyldisilazane are particularly preferable because they do not contain a fluorine atom and are low in cost.

Since all of the said manufacturing methods can be performed suitably in an organic solvent, as a result, the varnish of the polyimide precursor of this invention can be obtained easily.

The solvent used when manufacturing the polyimide precursor is, for example, N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imi Aprotic solvents such as dazolidinone and dimethyl sulfoxide are preferable, and N,N-dimethylacetamide and N-methyl-2-pyrrolidone are particularly preferable, but the raw material monomer component and the resulting polyimide precursor are dissolved. If it is, since any kind of solvent can be used without a problem, it is not specifically limited to the structure. As the solvent, an amide solvent such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, γ-butyrolactone, γ-valerolactone, δ-valerolactone, γ- Cyclic ester solvents, such as caprolactone, ε-caprolactone, and α-methyl-γ-butyrolactone, carbonate solvents such as ethylene carbonate and propylene carbonate, glycol solvents such as triethylene glycol, m- Phenolic solvents, such as cresol, p-cresol, 3-chlorophenol, 4-chlorophenol, acetophenone, 1, 3- dimethyl- 2-imidazolidinone, sulfolane, dimethyl sulfoxide, etc. are employ|adopted preferably. In addition, other common organic solvents such as phenol, o-cresol, butyl acetate, ethyl acetate, isobutyl acetate, propylene glycol methyl acetate, ethyl cellosolve, butyl cellosolve, 2-methyl cellosolve acetate, ethyl cell Losolv acetate, butyl cellosolve acetate, tetrahydrofuran, dimethoxyethane, diethoxyethane, dibutyl ether, diethylene glycol dimethyl ether, methyl isobutyl ketone, diisobutyl ketone, cyclopentanone, cyclohexanone, Methyl ethyl ketone, acetone, butanol, ethanol, xylene, toluene, chlorbenzene, terpene, mineral spirit, petroleum naphtha solvent, etc. can also be used. In addition, a solvent can also be used combining multiple types.

In this invention, although the logarithmic viscosity of a polyimide precursor is not specifically limited, The logarithmic viscosity in the N,N- dimethylacetamide solution with a density|concentration of 0.5 g/dL in 30 degreeC is 0.2 dL/g or more, More preferably It is preferably 0.8 dL/g or more, particularly preferably 0.9 dL/g or more. The molecular weight of a polyimide precursor is high that a logarithmic viscosity is 0.2 dL/g or more, and it is excellent in the mechanical strength and heat resistance of the polyimide obtained.

In the present invention, the varnish of the polyimide precursor (polyimide precursor solution composition) contains at least the polyimide precursor and the solvent of the present invention, and the total amount of the solvent, the tetracarboxylic acid component, and the diamine component is tetracarboxylic acid. It is suitable that the total amount of an acid component and a diamine component is a ratio of 5 mass % or more, Preferably it is 10 mass % or more, More preferably, it is 15 mass % or more. Moreover, it is usually 60 mass % or less, Preferably it is suitable that it is 50 mass % or less. Although this density|concentration is a density|concentration which approximates substantially to the solid content density|concentration resulting from a polyimide precursor, if this density|concentration is too low, for example, control of the film thickness of the polyimide film obtained when manufacturing a polyimide film becomes difficult. have.

As a solvent used for the varnish of the polyimide precursor of this invention, if a polyimide precursor melt|dissolves, there will be no problem, and the structure in particular will not be limited. As a varnish solvent of a polyimide precursor, the thing similar to the solvent used when manufacturing said polyimide precursor is mentioned, The solvent used when manufacturing a polyimide precursor can be used as a varnish solvent of a polyimide precursor as it is. Moreover, as needed, a solvent may be removed from the polyimide precursor solution manufactured as mentioned above, or you may add a solvent.

In the present invention, the varnish viscosity (rotational viscosity) of the polyimide precursor is not particularly limited, but the rotational viscosity measured using an E-type rotational viscometer at a temperature of 25° C. and a shear rate of 20 sec ⁻¹ is 0.01 to 1000 Pa· sec is preferable, and 0.1-100 Pa.sec is more preferable. Moreover, thixotropic property can also be provided as needed. In the viscosity of the said range, since it is easy to handle, when coating or film forming, repelling is suppressed and it is excellent in leveling property, a favorable film is obtained.

The varnish of the polyimide precursor of the present invention, if necessary, includes a chemical imidizing agent (acid anhydride such as acetic anhydride and amine compounds such as pyridine and isoquinoline), antioxidant, filler (inorganic particles such as silica), A dye, a pigment, a coupling agent such as a silane coupling agent, a primer, a flame retardant, an antifoaming agent, a leveling agent, a rheology control agent (flow aid), a release agent, and the like can be contained.

The polyimide of this invention can be suitably manufactured by carrying out the dehydration ring-closure reaction (imidization reaction) of the polyimide precursor of the above this invention. The method of imidation is not specifically limited, The method of well-known thermal imidation or chemical imidation is applicable suitably.

As for the form of the polyimide obtained, a film, a laminated body of a polyimide film and another base material, a coating film, powder, a bead, a molded object, a foam, a varnish, etc. are mentioned suitably.

Below, an example of the manufacturing method of the polyimide film/base material laminated body using the polyimide precursor of this invention, or a polyimide film is demonstrated. However, it is not limited to the following method.

Casting and applying the varnish of the polyimide precursor of the present invention on a substrate, in a vacuum, in an inert gas such as nitrogen, or in air, using hot air or infrared rays, 20 to 180° C., preferably 20 to 150° C. dry at a temperature range of Next, the obtained polyimide precursor film is peeled off the substrate or the polyimide precursor film is removed from the substrate, and in a state in which the end of the film is fixed, in a vacuum, in an inert gas such as nitrogen, or in air, hot air or infrared A polyimide film/substrate laminate or a polyimide film can be produced by heat imidization at a temperature of about 200 to 500°C, more preferably about 250 to 450°C. In addition, in order to prevent the polyimide film obtained from oxidative deterioration, it is preferable to perform heat imidation in vacuum or inert gas. As long as the temperature of heating imidization is not too high, even if it is carried out in air, there is no problem.

Here, it does not specifically limit as a base material, For example, base materials, such as a ceramic (glass, silicon, alumina), a metal (copper, aluminum, stainless steel), and a heat-resistant plastic film (polyimide film), can be used. In a certain embodiment, glass is preferable as a base material, and the polyimide film/glass base material laminated body which formed the polyimide film on the glass base material is used suitably in order to manufacture the board|substrate etc. for a display, for example.

In the imidization reaction of the polyimide precursor, instead of heat imidization by the heat treatment as described above, the polyimide precursor is subjected to a dehydration cyclization reagent such as acetic anhydride in the presence of a tertiary amine such as pyridine or triethylamine. It is also possible to carry out by chemical treatment such as immersion in a solution to be used. In addition, by pouring and stirring these dehydration cyclization reagents in advance in the varnish of the polyimide precursor, and casting and drying it on a substrate, a partially imidized polyimide precursor can also be produced, and this is further heat-treated as described above. , a polyimide film/substrate laminate, or a polyimide film can be obtained.

The polyimide of this invention makes a tetracarboxylic-acid component and a diamine component react further in a solvent, manufactures the solution composition (varnish) containing the polyimide of this invention, The polyimide solution composition manufactured by heating etc. It can also be suitably prepared by removing a solvent from it.

Hereinafter, an example of a method for producing a polyimide solution composition (varnish containing polyimide) of the present invention and a method for producing a polyimide film/substrate laminate or polyimide film using the polyimide solution composition will be described. . However, it is not limited to the following method.

In the polyimide solution composition of the present invention, in a solvent, a tetracarboxylic acid component such as tetracarboxylic dianhydride and a diamine component are approximately equimolar, preferably the molar ratio of the diamine component to the tetracarboxylic acid component [of the diamine component] The number of moles/the number of moles of the tetracarboxylic acid component] is preferably 0.90 to 1.10, more preferably 0.95 to 1.05, whereby it can be obtained suitably.

More specifically, a diamine component is dissolved in a solvent, and a tetracarboxylic acid component such as tetracarboxylic dianhydride is gradually added thereto while stirring in the solution, and, if necessary, preferably in the range of room temperature to 80°C. After stirring for 0.5 to 30 hours, the temperature is raised and imidation reaction is performed to obtain a polyimide solution. After adding a tetracarboxylic-acid component, it may heat up immediately and imidation reaction can also be performed. Moreover, it is also possible to reverse the addition order of a diamine component and a tetracarboxylic-acid component, and it is also possible to add a diamine component and a tetracarboxylic-acid component to a solvent simultaneously.

The method of imidation is not specifically limited, The method of well-known thermal imidation or chemical imidation is applicable suitably. For example, a solution containing a tetracarboxylic acid component such as tetracarboxylic dianhydride and a diamine component is heated to 100° C. or higher, preferably 120° C. or higher, more preferably at a temperature in the range of 150 to 250° C., The imidation reaction can be performed by stirring for 0.5-72 hours and making a tetracarboxylic-acid component and a diamine component react. In the case of chemical imidization, a chemical imidating agent (acid anhydride, such as acetic anhydride, and an amine compound, such as pyridine, isoquinoline, triethylamine) is added to a reaction solution, and it reacts. If necessary, an imidation catalyst or the like may be added to the reaction solution to perform the reaction.

Moreover, you may perform imidation reaction, removing the water produced|generated at the time of reaction.

When the molar ratio of the tetracarboxylic acid component and the diamine component is an excess of the diamine component, if necessary, a carboxylic acid derivative in an amount approximately equivalent to the number of excess moles of the diamine component is added, and the molar ratio of the tetracarboxylic acid component and the diamine component can be made close to approximately equivalent. Examples of the carboxylic acid derivative herein include tetracarboxylic acid that does not substantially increase the viscosity of the polyimide solution, that is, does not substantially participate in molecular chain extension, or tricarboxylic acid and its anhydride serving as a terminator; Dicarboxylic acids and their anhydrides are suitable.

The solvent used when manufacturing the polyimide solution is, for example, N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imi Aprotic solvents such as dazolidinone and dimethyl sulfoxide are preferable, and N,N-dimethylacetamide and N-methyl-2-pyrrolidone are particularly preferable, but when the raw material monomer component and the resulting polyimide are dissolved, , since any kind of solvent can be used without any problem, it is not particularly limited to its structure. As the solvent, an amide solvent such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, γ-butyrolactone, γ-valerolactone, δ-valerolactone, γ- Cyclic ester solvents, such as caprolactone, ε-caprolactone, and α-methyl-γ-butyrolactone, carbonate solvents such as ethylene carbonate and propylene carbonate, glycol solvents such as triethylene glycol, m- Phenolic solvents, such as cresol, p-cresol, 3-chlorophenol, 4-chlorophenol, acetophenone, 1, 3- dimethyl- 2-imidazolidinone, sulfolane, dimethyl sulfoxide, etc. are employ|adopted preferably. In addition, other common organic solvents such as phenol, o-cresol, butyl acetate, ethyl acetate, isobutyl acetate, propylene glycol methyl acetate, ethyl cellosolve, butyl cellosolve, 2-methyl cellosolve acetate, ethyl cell Losolv acetate, butyl cellosolve acetate, tetrahydrofuran, dimethoxyethane, diethoxyethane, dibutyl ether, diethylene glycol dimethyl ether, methyl isobutyl ketone, diisobutyl ketone, cyclopentanone, cyclohexanone, Methyl ethyl ketone, acetone, butanol, ethanol, xylene, toluene, chlorbenzene, terpene, mineral spirit, petroleum naphtha solvent, etc. can also be used. In addition, a solvent can also be used combining multiple types.

After performing the imidation reaction as mentioned above, the obtained reaction solution can be used as a polyimide solution composition of this invention by adding the additive etc. which are mentioned later as it is, or by concentration or dilution as needed. Or the polyimide solution composition (varnish) of this invention can also be obtained by isolating a soluble polyimide from the obtained reaction solution, adding the isolated polyimide to a solvent. Isolation of a polyimide can be performed, for example by dripping or mixing the reaction solution containing the obtained soluble polyimide with poor solvents, such as water, and precipitating (reprecipitating) a polyimide.

The polyimide solution composition (polyimide varnish) of the present invention contains at least the polyimide of the present invention and a solvent, and the polyimide content is 5% by mass or more, preferably 10% by mass, based on the total amount of the solvent and the polyimide. Above, more preferably 15 mass % or more, Especially preferably, it is suitable that it is a ratio of 20 mass % or more. When this density|concentration is too low, control of the film thickness of the polyimide film obtained when manufacturing a polyimide film, for example may become difficult. Moreover, it is usually 60 mass % or less of polyimide, Preferably it is suitable that it is 50 mass % or less.

As a solvent of the polyimide solution composition of this invention, if a polyimide melt|dissolves, there will be no problem, Especially the structure is not limited. As a solvent of a polyimide solution composition, the thing similar to the solvent used when manufacturing the said polyimide solution is mentioned, The solvent used when manufacturing a polyimide solution can be used as a solvent of a polyimide solution composition as it is. Moreover, you may remove a solvent from the polyimide solution composition manufactured as mentioned above as needed, or you may add a solvent.

In the present invention, although the logarithmic viscosity of the polyimide is not particularly limited, the logarithmic viscosity in a N,N-dimethylacetamide solution having a concentration of 0.5 g/dL at 30°C is 0.2 dL/g or more, more preferably is 0.4 dL/g or more, particularly preferably 0.5 dL/g or more. It is excellent in the mechanical strength and heat resistance of the polyimide obtained as logarithmic viscosity is 0.2 dL/g or more.

In the present invention, the viscosity (rotational viscosity) of the polyimide solution composition is not particularly limited, but the rotational viscosity measured using an E-type rotational viscometer at a temperature of 25° C. and a shear rate of 20 sec ⁻¹ is 0.01 to 1000 Pa· sec is preferable, and 0.1-100 Pa.sec is more preferable. Moreover, thixotropic property can also be provided as needed. In the viscosity of the said range, since it is easy to handle, when coating or film forming, repelling is suppressed and it is excellent in leveling property, a favorable film is obtained.

The polyimide solution composition of the present invention, if necessary, contains antioxidants, fillers (inorganic particles such as silica), dyes, pigments, coupling agents such as silane coupling agents, primers, flame retardants, defoamers, leveling agents, rheology control agent (flow aid), release agent, etc. can be contained.

The polyimide of this invention can be obtained suitably by removing a solvent from the polyimide solution composition manufactured as mentioned above. For example, a polyimide film/substrate laminate can be manufactured by casting and apply|coating a polyimide solution composition on a base material, heating a polyimide solution composition on a base material, and removing a solvent. Although the temperature of heat processing is not specifically limited, Usually, it is 80-500 degreeC, Preferably it is 100-500 degreeC, More preferably, it is the temperature of about 150-450 degreeC. Although the heat treatment can be performed in a vacuum, in an inert gas such as nitrogen, or in air, it is usually preferable to perform the heat treatment in a vacuum or in an inert gas. And a polyimide film can be manufactured by peeling the polyimide film formed on this base material from a base material.

Here, it does not specifically limit as a base material, For example, base materials, such as a ceramic (glass, silicon, alumina), a metal (copper, aluminum, stainless steel), and a heat-resistant plastic film (polyimide film), can be used. In a certain embodiment, glass is preferable as a base material, and the polyimide film/glass base material laminated body which formed the polyimide film on the glass base material is used suitably in order to manufacture the board|substrate etc. for a display, for example.

Further, the polyimide solution composition was cast and applied on the substrate, the polyimide solution composition on the substrate was dried to the extent that it became self-supporting, and the obtained self-supporting film was peeled from the substrate, and the end of the film was fixed. A polyimide film can be suitably manufactured also by heating in a state and removing a solvent. Although the drying conditions at the time of manufacturing a self-supporting film can be set suitably, For example, what is necessary is just to dry a polyimide solution composition on a base material in the temperature range of about 50-300 degreeC. Although the heat processing temperature of a self-supporting film is not specifically limited, Usually, it is 80-500 degreeC, Preferably it is 100-500 degreeC, More preferably, it is a temperature of about 150-480 degreeC. Also in this method, although heat processing can be performed in vacuum, in inert gas, such as nitrogen, or air, it is usually preferable to perform in vacuum or inert gas.

In addition, the form of the polyimide obtained from a polyimide solution composition is not limited to a film, a laminated body of a polyimide film, and another base material, A coating film, powder, beads, a molded object, a foam, etc. are mentioned suitably.

The polyimide of the present invention obtained in this way has a coefficient of linear thermal expansion between 100 and 250°C when measured on a film having a thickness of 10 µm, is not particularly limited, but is preferably 40 ppm/K or less, more preferably It is preferable that it is 35 ppm/K or less, More preferably, it is 30 ppm/K or less, Especially preferably, it is 25 ppm/K or less. When a linear thermal expansion coefficient is large, the difference of linear thermal expansion coefficient with conductors, such as a metal, is large, and when a circuit board is formed, problems, such as an increase in curvature, may arise.

In the polyimide of the present invention, the light transmittance at a wavelength of 400 nm when measured with a film having a thickness of 10 µm is not particularly limited, but is preferably 80% or more, more preferably 83% or more, particularly preferably is preferably 85% or more. When using a polyimide film for a display use etc., when a light transmittance is low, it is necessary to make a light source strong, and the problem that energy is required, etc. may arise.

The polyimide of the present invention has a haze measured on a film having a thickness of 10 µm, is not particularly limited, but is preferably 2% or less, more preferably 1.5% or less, particularly preferably 1% or less. do. When a polyimide film is used for a display use etc., when a haze is high, light may scatter and an image may become blurred.

The thickness direction retardation (Rth) of the polyimide of the present invention when measured with a film having a thickness of 10 µm is not particularly limited, but is preferably 500 nm or less, more preferably 350 nm or less, particularly preferably It is preferable that it is 400 nm or less. When a polyimide film is used for a display purpose, etc., if the retardation in the thickness direction is large, the problem that the color of transmitted light is not displayed correctly, a color spreads, and a viewing angle narrows may arise.

Although the film containing the polyimide of the present invention varies depending on the application, the thickness of the film is preferably 1 µm to 250 µm, more preferably 1 µm to 150 µm, still more preferably 1 µm to 100 µm, Especially preferably, it is 1 micrometer - 80 micrometers. In the case where the polyimide film is used for light transmission, if the polyimide film is too thick, the light transmittance may decrease.

A flexible conductive substrate can be obtained by forming an electroconductive layer on the single side|surface or both surfaces of the polyimide film/base material laminated body obtained by making it above, or a polyimide film.

A flexible conductive substrate can be obtained by the following method, for example. That is, as the first method, the polyimide film/substrate laminate is applied to the surface of the polyimide film without peeling the polyimide film from the substrate by sputtering, vapor deposition, printing, etc. , conductive carbon, etc.) is formed to prepare a conductive laminate of conductive layer/polyimide film/substrate. After that, if necessary, by peeling the conductive layer/polyimide film laminate from the base material, a transparent and flexible conductive substrate including the conductive layer/polyimide film laminate can be obtained.

As the second method, the polyimide film is peeled from the substrate of the polyimide film/substrate laminate to obtain a polyimide film, and a conductive material (metal or metal oxide, conductive organic substance, conductive carbon, etc.) is applied to the surface of the polyimide film. By forming the conductive layer in the same manner as in the first method, a transparent and flexible conductive substrate comprising a conductive layer/polyimide film laminate or a conductive layer/polyimide film/conductive layer laminate can be obtained.

In addition, in the first and second methods, if necessary, before forming the conductive layer on the surface of the polyimide film, by sputtering, vapor deposition, gel-sol method, or the like, a gas barrier layer such as water vapor or oxygen, a light control layer You may form inorganic layers, such as these.

In addition, a circuit is suitably formed in the conductive layer by methods, such as the photolithography method, various printing methods, and the inkjet method.

The board|substrate of this invention obtained in this way has the circuit of a conductive layer through a gas barrier layer and an inorganic layer as needed on the surface of the polyimide film comprised with the polyimide of this invention. Since this board|substrate is flexible, it is excellent in high transparency, bendability, and heat resistance, and also has a low coefficient of linear thermal expansion, formation of a fine circuit is easy. Accordingly, this substrate can be suitably used as a substrate for a display, a touch panel, or a solar cell.

That is, transistors (inorganic transistors, organic transistors) are further formed on this substrate by vapor deposition, various printing methods, inkjet methods, or the like to produce flexible thin film transistors, and liquid crystal elements for display devices, EL elements, and photoelectric elements. is appropriately used as

Further, in the first method, after forming at least a part of not only the conductive layer but also other elements and structures required for the transistor and/or device on the surface of the polyimide film/substrate laminate, the substrate may be peeled off .

Example

Hereinafter, the present invention will be further described by way of Examples and Comparative Examples. In addition, this invention is not limited to a following example.

In each of the following examples, evaluation was performed by the following method.

<Evaluation of polyimide film>

[400nm light transmittance]

The light transmittance in wavelength 400nm of the polyimide film of the film thickness of 10 micrometers and the square size whose one side is 5 cm was measured using ultraviolet-visible spectrophotometer /V-650DS (made by Nippon Bunko).

[Heize]

Using a turbidimeter/NDH2000 (manufactured by Nippon Denshoku Kogyo Co., Ltd.), the haze of a polyimide film having a thickness of 10 µm and a square size of 5 cm on one side was measured in accordance with the standard of JIS K7136.

[Coefficient of linear thermal expansion (CTE)]

A 10 µm-thick polyimide film was cut out into a 4 mm wide rectangle to be a test piece, and TMA/SS6100 (manufactured by SII Nanotechnology Co., Ltd.) was used, with a distance between chucks of 15 mm, a tensile load of 2 g, and a temperature increase rate of 20°C. It heated up to 500 degreeC at /min. From the obtained TMA curve, the linear thermal expansion coefficient from 100 degreeC to 250 degreeC was calculated|required.

[Film thickness direction retardation (R _th )]

Using a polyimide film having a film thickness of 10 µm and a square size of 5 cm as a test piece, using a retardation measuring apparatus (KOBRA-WR) manufactured by Oji Keisoku Co., Ltd., the retardation of the film was measured at an angle of incidence of 40°. did. From the obtained retardation, the retardation in the thickness direction of the film with a film thickness of 10 micrometers was calculated|required.

[Tensile modulus, elongation at break, stress at break]

The polyimide film was punched into a dumbbell shape of the IEC-540(S) standard to obtain a test piece (width: 4 mm), and using TENSILON manufactured by ORIENTEC, the length between chucks was 30 mm, the tensile rate was 2 mm/min, and the initial tensile The elastic modulus, elongation at break, and stress at break were measured.

The abbreviation, purity, etc. of the raw material used in the following each example are as follows.

[Diamine component]

TFMB: 2,2'-bis(trifluoromethyl)benzidine [purity: 99.83% (GC analysis)]

BAFL: 9,9-bis(4-aminophenyl)fluorene

4,4'-ODA: 4,4'-oxydianiline [purity: 99.9% (GC analysis)]

BAPB: 4,4'-bis(4-aminophenoxy)biphenyl

SFXO: 4,4'-(spiro[fluorene-9,9'-xanthene]-3',6'-diylbis(oxy))dianiline

[Tetracarboxylic acid component]

CpODA: norbornane-2-spiro-α-cyclopentanone-α′-spiro-2″-norbornane-5,5″,6,6″-tetracarboxylic dianhydride

PMDA-H: 1,2,4,5-cyclohexanetetracarboxylic dianhydride [purity: 99.9% (GC analysis)]

a-BPDA: 2,3,3',4'-biphenyltetracarboxylic dianhydride

[menstruum]

GBL: γ-butyrolactone

DMAc: N,N-dimethylacetamide

Table 1 shows the structural formulas of the tetracarboxylic acid component and the diamine component used in Examples and Comparative Examples.

[Example 1]

In a reaction vessel substituted with nitrogen gas, 1.70 g (5.3 mmol) of TFMB and 7.40 g (21.3 mmol) of BAFL were put, and DMAc was added so that the total mass of the charged monomer (the sum of the diamine component and the carboxylic acid component) was 25% by mass. An amount of 94.24 g was added, followed by stirring at room temperature for 1 hour. To this solution, 10.20 g (26.5 mmol) of CpODA was slowly added. The mixture was stirred at 70°C for 3 hours and at 160°C for 7 hours to obtain a uniform and viscous polyimide solution. The imidation ratio of the obtained polyimide solution was 95 % or more.

The polyimide solution was apply|coated to a glass substrate, and under nitrogen atmosphere (oxygen concentration 200 ppm or less), it heated from room temperature to 410 degreeC as it is on a glass substrate, the solvent was removed, and the colorless and transparent polyimide film/glass laminated body was obtained. Next, after immersing the obtained polyimide film/glass laminated body in water, it peeled and dried, and obtained the polyimide film whose film thickness is 10 micrometers.

The result of having measured the characteristic of this polyimide film is shown in Table 2-1.

[Example 2]

In a reaction vessel substituted with nitrogen gas, 3.00 g (9.4 mmol) of TFMB and 6.06 g (17.4 mmol) of BAFL were put, and DMAc was added so that the total mass of the charged monomer (sum of the diamine component and the carboxylic acid component) was 17% by mass. An amount of 94.48 g was added, and the mixture was stirred at room temperature for 1 hour. To this solution, 10.29 g (26.8 mmol) of CpODA was slowly added. The mixture was stirred at 70°C for 3 hours and at 160°C for 7 hours to obtain a uniform and viscous polyimide solution. The imidation ratio of the obtained polyimide solution was 95 % or more.

The polyimide solution was apply|coated to a glass substrate, and under nitrogen atmosphere (oxygen concentration 200 ppm or less), it heated from room temperature to 410 degreeC as it is on a glass substrate, the solvent was removed, and the colorless and transparent polyimide film/glass laminated body was obtained. Next, after immersing the obtained polyimide film/glass laminated body in water, it peeled and dried, and obtained the polyimide film whose film thickness is 10 micrometers.

The result of having measured the characteristic of this polyimide film is shown in Table 2-1.

[Example 3]

In a reaction vessel substituted with nitrogen gas, 7.00 g (21.9 mmol) of TFMB and 7.62 g (21.9 mmol) of BAFL were put, and DMAc was added so that the total mass of the charged monomer (the sum of the diamine component and the carboxylic acid component) was 25% by mass. An amount of 94.26 g was added, and the mixture was stirred at room temperature for 1 hour. To this solution, 16.80 g (43.7 mmol) of CpODA was slowly added. The mixture was stirred at 70°C for 3 hours and at 160°C for 7 hours to obtain a uniform and viscous polyimide solution. The imidation ratio of the obtained polyimide solution was 95 % or more.

The polyimide solution was apply|coated to a glass substrate, and under nitrogen atmosphere (oxygen concentration 200 ppm or less), it heated from room temperature to 410 degreeC as it is on a glass substrate, the solvent was removed, and the colorless and transparent polyimide film/glass laminated body was obtained. Next, after immersing the obtained polyimide film/glass laminated body in water, it peeled and dried, and obtained the polyimide film whose film thickness is 10 micrometers.

The result of having measured the characteristic of this polyimide film is shown in Table 2-1.

[Example 4]

In a reaction vessel substituted with nitrogen gas, 7.00 g (21.9 mmol) of TFMB and 6.23 g (17.9 mmol) of BAFL were put, and a mixed solvent of DMAc and GBL (DMAc:GBL=1:2 (weight ratio)) was added, and the total mass of the charged monomers. 95.44 g (31.81 g of DMAc and 63.63 g of GBL) which is a quantity used as 23 mass % (total of a diamine component and a carboxylic acid component) was added, and it stirred at room temperature for 1 hour. To this solution, 15.28 g (39.7 mmol) of CpODA was slowly added. The mixture was stirred at 70°C for 3 hours and at 160°C for 7 hours to obtain a uniform and viscous polyimide solution. The imidation ratio of the obtained polyimide solution was 95 % or more.

The polyimide solution was apply|coated to a glass substrate, and under nitrogen atmosphere (oxygen concentration 200 ppm or less), it heated from room temperature to 450 degreeC as it is on a glass substrate, the solvent was removed, and the colorless and transparent polyimide film/glass laminated body was obtained. Next, after immersing the obtained polyimide film/glass laminated body in water, it peeled and dried, and obtained the polyimide film whose film thickness is 10 micrometers.

The result of having measured the characteristic of this polyimide film is shown in Table 2-1.

[Example 5]

In a reaction vessel substituted with nitrogen gas, 9.00 g (28.1 mmol) of TFMB and 6.53 g (18.7 mmol) of BAFL were put, and DMAc was added so that the total mass of the charged monomer (the sum of the diamine component and the carboxylic acid component) was 23% by mass. 112.26 g of the quantity was added, and it stirred at room temperature for 1 hour. 18.00 g (46.8 mmol) of CpODA was slowly added to this solution. The mixture was stirred at 70°C for 3 hours and at 160°C for 7 hours to obtain a uniform and viscous polyimide solution. The imidation ratio of the obtained polyimide solution was 95 % or more.

The polyimide solution was applied to a glass substrate, and under a nitrogen atmosphere (oxygen concentration of 200 ppm or less), the solvent was removed by heating from room temperature to 430° C. on the glass substrate as it was, to obtain a colorless and transparent polyimide film/glass laminate. Next, after immersing the obtained polyimide film/glass laminated body in water, it peeled and dried, and obtained the polyimide film whose film thickness is 10 micrometers.

The result of having measured the characteristic of this polyimide film is shown in Table 2-1.

[Example 6]

In a reaction vessel substituted with nitrogen gas, 9.00 g (28.1 mmol) of TFMB and 4.20 g (12.0 mmol) of BAFL were put, and DMAc was added so that the total mass of the charged monomer (the sum of the diamine component and the carboxylic acid component) was 23% by mass. 95.85 g of the quantity was added, and it stirred at room temperature for 1 hour. To this solution, 15.43 g (40.2 mmol) of CpODA was slowly added. The mixture was stirred at 70°C for 3 hours and at 160°C for 7 hours to obtain a uniform and viscous polyimide solution. The imidation ratio of the obtained polyimide solution was 95 % or more.

The polyimide solution was apply|coated to a glass substrate, and under nitrogen atmosphere (oxygen concentration 200 ppm or less), it heated from room temperature to 410 degreeC as it is on a glass substrate, the solvent was removed, and the colorless and transparent polyimide film/glass laminated body was obtained. Next, after immersing the obtained polyimide film/glass laminated body in water, it peeled and dried, and obtained the polyimide film whose film thickness is 10 micrometers.

The result of having measured the characteristic of this polyimide film is shown in Table 2-1.

[Example 7]

In a reaction vessel substituted with nitrogen gas, 10.00 g (31.2 mmol) of TFMB and 2.72 g (7.8 mmol) of BAFL were put, and DMAc was added so that the total mass of the charged monomer (the sum of the diamine component and the carboxylic acid component) was 23% by mass. 92.82 g of the quantity was added, and it stirred at room temperature for 1 hour. To this solution, 15.00 g (39.0 mmol) of CpODA was slowly added. The mixture was stirred at 70°C for 3 hours and at 160°C for 7 hours to obtain a uniform and viscous polyimide solution. The imidation ratio of the obtained polyimide solution was 95 % or more.

The polyimide solution was apply|coated to a glass substrate, and under nitrogen atmosphere (oxygen concentration 200 ppm or less), it heated from room temperature to 410 degreeC as it is on a glass substrate, the solvent was removed, and the colorless and transparent polyimide film/glass laminated body was obtained. Next, after immersing the obtained polyimide film/glass laminated body in water, it peeled and dried, and obtained the polyimide film whose film thickness is 10 micrometers.

The result of having measured the characteristic of this polyimide film is shown in Table 2-1.

[Example 8]

In a reaction vessel substituted with nitrogen gas, 8.00 g (25.0 mmol) of TFMB, 2.90 g (8.3 mmol) of BAFL, and 1.67 g (8.3 mmol) of 4,4'-ODA were put, and DMAc was added to the total mass of the charged monomer (diamine component and 95.66 g which is the quantity used as 23 mass % (total of carboxylic acid components) was added, and it stirred at room temperature for 1 hour. To this solution, 16.00 g (41.6 mmol) of CpODA was slowly added. The mixture was stirred at 70°C for 3 hours and at 160°C for 7 hours to obtain a uniform and viscous polyimide solution. The imidation ratio of the obtained polyimide solution was 95 % or more.

The polyimide solution was apply|coated to a glass substrate, and under nitrogen atmosphere (oxygen concentration 200 ppm or less), it heated from room temperature to 410 degreeC as it is on a glass substrate, the solvent was removed, and the colorless and transparent polyimide film/glass laminated body was obtained. Next, after immersing the obtained polyimide film/glass laminated body in water, it peeled and dried, and obtained the polyimide film whose film thickness is 10 micrometers.

The result of having measured the characteristic of this polyimide film is shown in Table 2-1.

[Example 9]

In a reaction vessel substituted with nitrogen gas, 8.00 g (25.0 mmol) of TFMB, 4.35 g (12.5 mmol) of BAFL, and 1.53 g (4.2 mmol) of BAPB were put, and DMAc was added to the total mass of the charged monomer (diamine component and carboxylic acid component). 100.07 g which is the quantity used as 23 mass % of total) was added, and it stirred at room temperature for 1 hour. To this solution, 16.00 g (41.6 mmol) of CpODA was slowly added. The mixture was stirred at 70°C for 3 hours and at 160°C for 7 hours to obtain a uniform and viscous polyimide solution. The imidation ratio of the obtained polyimide solution was 95 % or more.

The polyimide solution was apply|coated to a glass substrate, and under nitrogen atmosphere (oxygen concentration 200 ppm or less), it heated from room temperature to 410 degreeC as it is on a glass substrate, the solvent was removed, and the colorless and transparent polyimide film/glass laminated body was obtained. Next, after immersing the obtained polyimide film/glass laminated body in water, it peeled and dried, and obtained the polyimide film whose film thickness is 10 micrometers.

The result of having measured the characteristic of this polyimide film is shown in Table 2-1.

[Example 10]

In a reaction vessel substituted with nitrogen gas, 6.00 g (18.7 mmol) of TFMB and 8.38 g (15.3 mmol) of SFXO were put, and a mixed solvent of DMAc and GBL (DMAc:GBL=1:2 (weight ratio)) was added, and the total mass of the charged monomers. 82.44 g (27.48 g of DMAc and 54.96 g of GBL) which is a quantity used as 25 mass % (total of a diamine component and a carboxylic acid component) was added, and it stirred at room temperature for 1 hour. 13.09 g (34.1 mmol) of CpODA was slowly added to this solution. The mixture was stirred at 70°C for 3 hours and at 160°C for 7 hours to obtain a uniform and viscous polyimide solution. The imidation ratio of the obtained polyimide solution was 95 % or more.

The polyimide solution was apply|coated to a glass substrate, and under nitrogen atmosphere (oxygen concentration 200 ppm or less), it heated from room temperature to 410 degreeC as it is on a glass substrate, the solvent was removed, and the colorless and transparent polyimide film/glass laminated body was obtained. Next, after immersing the obtained polyimide film/glass laminated body in water, it peeled and dried, and obtained the polyimide film whose film thickness is 10 micrometers.

The result of having measured the characteristic of this polyimide film is shown in Table 2-1.

[Example 11]

In a reaction vessel substituted with nitrogen gas, 11.00 g (34.4 mmol) of TFMB and 5.13 g (14.7 mmol) of BAFL were put, and a mixed solvent of DMAc and GBL (DMAc:GBL=1:2 (weight ratio)) was added, and the total mass of the charged monomers. 87.29g (DMAc 29.10g and GBL 58.19g) which is the quantity used as 25 mass % (total of a diamine component and a carboxylic acid component) was added, and it stirred at room temperature for 1 hour. To this solution, 4.72 g (12.3 mmol) of CpODA and 8.25 g (36.8 mmol) of PMDA-H were gradually added. The mixture was stirred at 70°C for 3 hours and at 160°C for 7 hours to obtain a uniform and viscous polyimide solution. The imidation ratio of the obtained polyimide solution was 95 % or more.

The polyimide solution was apply|coated to a glass substrate, and under nitrogen atmosphere (oxygen concentration 200 ppm or less), it heated from room temperature to 410 degreeC as it is on a glass substrate, the solvent was removed, and the colorless and transparent polyimide film/glass laminated body was obtained. Next, after immersing the obtained polyimide film/glass laminated body in water, it peeled and dried, and obtained the polyimide film whose film thickness is 10 micrometers.

The result of having measured the characteristic of this polyimide film is shown in Table 2-2.

[Example 12]

In a reaction vessel substituted with nitrogen gas, 10.00 g (31.2 mmol) of TFMB and 4.66 g (13.4 mmol) of BAFL were put, and a mixed solvent of DMAc and GBL (DMAc:GBL=1:2 (weight ratio)) was added, and the total mass of the charged monomers. 84.71 g (28.24 g of DMAc and 56.47 g of GBL) which is a quantity used as 25 mass % (total of a diamine component and a carboxylic acid component) was added, and it stirred at room temperature for 1 hour. CpODA 8.57 g (22.3 mmol) and PMDA-H 5.00 g (22.3 mmol) were gradually added to this solution. The mixture was stirred at 70°C for 3 hours and at 160°C for 7 hours to obtain a uniform and viscous polyimide solution. The imidation ratio of the obtained polyimide solution was 95 % or more.

The polyimide solution was apply|coated to a glass substrate, and under nitrogen atmosphere (oxygen concentration 200 ppm or less), it heated from room temperature to 410 degreeC as it is on a glass substrate, the solvent was removed, and the colorless and transparent polyimide film/glass laminated body was obtained. Next, after immersing the obtained polyimide film/glass laminated body in water, it peeled and dried, and obtained the polyimide film whose film thickness is 10 micrometers.

The result of having measured the characteristic of this polyimide film is shown in Table 2-2.

[Example 13]

In a reaction vessel substituted with nitrogen gas, 10.00 g (31.2 mmol) of TFMB and 4.66 g (13.4 mmol) of BAFL were put, and a mixed solvent of DMAc and GBL (DMAc:GBL=1:2 (weight ratio)) was added, and the total mass of the charged monomers. 90.06 g (30.02 g of DMAc and 60.04 g of GBL) which is a quantity used as 25 mass % (total of a diamine component and a carboxylic acid component) was added, and it stirred at room temperature for 1 hour. To this solution, 12.86 g (33.5 mmol) of CpODA and 2.50 g (11.1 mmol) of PMDA-H were gradually added. The mixture was stirred at 70°C for 3 hours and at 160°C for 7 hours to obtain a uniform and viscous polyimide solution. The imidation ratio of the obtained polyimide solution was 95 % or more.

The polyimide solution was apply|coated to a glass substrate, and under nitrogen atmosphere (oxygen concentration 200 ppm or less), it heated from room temperature to 410 degreeC as it is on a glass substrate, the solvent was removed, and the colorless and transparent polyimide film/glass laminated body was obtained. Next, after immersing the obtained polyimide film/glass laminated body in water, it peeled and dried, and obtained the polyimide film whose film thickness is 10 micrometers.

The result of having measured the characteristic of this polyimide film is shown in Table 2-2.

[Example 14]

In a reaction vessel substituted with nitrogen gas, 7.50 g (23.4 mmol) of TFMB and 8.16 g (23.4 mmol) of BAFL were put, and a mixed solvent of DMAc and GBL (DMAc:GBL=1:2 (weight ratio)) was added, and the total mass of the charged monomers. 95.40 g (31.80 g of DMAc and 63.60 g of GBL) which is the quantity used as 25 mass % (total of a diamine component and a carboxylic acid component) was added, and it stirred at room temperature for 1 hour. To this solution, 13.50 g (35.1 mmol) of CpODA and 2.63 g (11.7 mmol) of PMDA-H were gradually added. The mixture was stirred at 70°C for 3 hours and at 160°C for 7 hours to obtain a uniform and viscous polyimide solution. The imidation ratio of the obtained polyimide solution was 95 % or more.

The polyimide solution was apply|coated to a glass substrate, and under nitrogen atmosphere (oxygen concentration 200 ppm or less), it heated from room temperature to 410 degreeC as it is on a glass substrate, the solvent was removed, and the colorless and transparent polyimide film/glass laminated body was obtained. Next, after immersing the obtained polyimide film/glass laminated body in water, it peeled and dried, and obtained the polyimide film whose film thickness is 10 micrometers.

The result of having measured the characteristic of this polyimide film is shown in Table 2-2.

[Example 15]

In a reaction vessel substituted with nitrogen gas, 8.00 g (25.0 mmol) of TFMB and 8.70 g (25.0 mmol) of BAFL were put, and a mixed solvent of DMAc and GBL (DMAc:GBL=1:2 (weight ratio)) was added, and the total mass of the charged monomers. 95.73 g (31.91 g of DMAc and 63.82 g of GBL) which is a quantity used as 25 mass % (total of a diamine component and a carboxylic acid component) was added, and it stirred at room temperature for 1 hour. To this solution, 13.50 g (25.0 mmol) of CpODA and 2.63 g (25.0 mmol) of PMDA-H were gradually added. The mixture was stirred at 70°C for 3 hours and at 160°C for 7 hours to obtain a uniform and viscous polyimide solution. The imidation ratio of the obtained polyimide solution was 95 % or more.

The polyimide solution was apply|coated to a glass substrate, and under nitrogen atmosphere (oxygen concentration 200 ppm or less), it heated from room temperature to 410 degreeC as it is on a glass substrate, the solvent was removed, and the colorless and transparent polyimide film/glass laminated body was obtained. Next, after immersing the obtained polyimide film/glass laminated body in water, it peeled and dried, and obtained the polyimide film whose film thickness is 10 micrometers.

The result of having measured the characteristic of this polyimide film is shown in Table 2-2.

[Example 16]

In a reaction vessel substituted with nitrogen gas, 15.00 g (46.8 mmol) of TFMB was put, a mixed solvent of DMAc and GBL (DMAc:GBL=1:2 (weight ratio)), and the total mass of the charged monomers (diamine component and carboxylic acid component) 90.00 g (30.00 g of DMAc and 60.00 g of GBL) which is an amount used as 25 mass % (total of) was added, and it stirred at room temperature for 1 hour. To this solution, 10.80 g (28.1 mmol) of CpODA and 4.20 g (18.7 mmol) of PMDA-H were gradually added. The mixture was stirred at 70°C for 3 hours and at 160°C for 7 hours to obtain a uniform and viscous polyimide solution. The imidation ratio of the obtained polyimide solution was 95 % or more.

The polyimide solution was apply|coated to a glass substrate, and under nitrogen atmosphere (oxygen concentration 200 ppm or less), it heated from room temperature to 370 degreeC as it is on a glass substrate, the solvent was removed, and the colorless and transparent polyimide film/glass laminated body was obtained. Next, after immersing the obtained polyimide film/glass laminated body in water, it peeled and dried, and obtained the polyimide film whose film thickness is 10 micrometers.

The result of having measured the characteristic of this polyimide film is shown in Table 2-2.

[Example 17]

In a reaction vessel substituted with nitrogen gas, 15.00 g (46.8 mmol) of TFMB was put, a mixed solvent of DMAc and GBL (DMAc:GBL=1:2 (weight ratio)), and the total mass of the charged monomers (diamine component and carboxylic acid component) 93.95 g (31.32 g of DMAc and 62.63 g of GBL) which is the quantity used as 25 mass % (sum of total) was added, and it stirred at room temperature for 1 hour. To this solution, 10.80 g (28.1 mmol) of CpODA and 5.51 g (18.7 mmol) of a-BPDA were slowly added. The mixture was stirred at 70°C for 3 hours and at 160°C for 7 hours to obtain a uniform and viscous polyimide solution. The imidation ratio of the obtained polyimide solution was 95 % or more.

The polyimide solution was apply|coated to a glass substrate, and under nitrogen atmosphere (oxygen concentration 200 ppm or less), it heated from room temperature to 410 degreeC as it is on a glass substrate, the solvent was removed, and the colorless and transparent polyimide film/glass laminated body was obtained. Next, after immersing the obtained polyimide film/glass laminated body in water, it peeled and dried, and obtained the polyimide film whose film thickness is 10 micrometers.

The result of having measured the characteristic of this polyimide film is shown in Table 2-2.

[Comparative Example 1]

In a reaction vessel substituted with nitrogen gas, 40.00 g (124.9 mmol) of TFMB was put, a mixed solvent of DMAc and GBL (DMAc:GBL=1:2 (weight ratio)), the total mass of the charged monomers (diamine component and carboxylic acid component) 264.04 g (DMAc of 88.01 g and GBL of 176.03 g) which is an amount used as 25 mass %) was added, and it stirred at room temperature for 1 hour. To this solution, 48.01 g (124.9 mmol) of CpODA was slowly added. The mixture was stirred at 70°C for 3 hours and at 160°C for 7 hours to obtain a uniform and viscous polyimide solution. The imidation ratio of the obtained polyimide solution was 95 % or more.

The polyimide solution was apply|coated to a glass substrate, and under nitrogen atmosphere (oxygen concentration 200 ppm or less), it heated from room temperature to 410 degreeC as it is on a glass substrate, the solvent was removed, and the colorless and transparent polyimide film/glass laminated body was obtained. Next, after immersing the obtained polyimide film/glass laminated body in water, it peeled and dried, and obtained the polyimide film whose film thickness is 10 micrometers.

The result of having measured the characteristic of this polyimide film is shown in Table 2-2.

[Table 2-1]

[Table 2-2]

ADVANTAGE OF THE INVENTION According to this invention, it has high transparency, a low coefficient of linear thermal expansion, and can provide the polyimide with a small thickness direction retardation (retardation), and its precursor. The polyimide obtained from the polyimide precursor of the present invention and the polyimide of the present invention have high transparency, low coefficient of linear thermal expansion, easy formation of fine circuits, and small thickness-direction retardation, particularly for display applications. In order to form board|substrates, such as these, it can use suitably.

Claims (7)

As a polyimide precursor comprising a repeating unit represented by the following general formula (1),
A ₁ in the following general formula (1) includes a tetravalent group represented by the following formula (A-1), and B ₁ in the following general formula (1) is a divalent group represented by the following formula (B-1) including,
Furthermore, B ₁ of the following general formula (1) contains a divalent group containing a structure represented by the following formula (2), and A ₁ of the following general formula (1) is represented by the following formula (2) It may include at least one selected from a tetravalent group including the structure represented by the following formula (3) and a tetravalent group represented by the following formula (4),
A tetravalent group represented by the formula (A-1) in 100 mol% of A ₁ in the general formula (1), a tetravalent group containing a structure represented by the formula (2), a tetravalent group represented by the formula (3) , and the content ratio of the sum of the tetravalent groups represented by the formula (4), the divalent group represented by the formula (B-1) in 100 mol% of B ₁ in the general formula (1), and the formula (2) The sum of the content ratio of the sum of the divalent groups including the structure shown is 120 mol% or more,
However, the tetravalent group represented by Formula (A-1), the tetravalent group containing the structure represented by Formula (2), the tetravalent group represented by Formula (3), and 4 represented by Formula (4) The ratio of the tetravalent group including the structure represented by formula (2), the tetravalent group represented by the formula (3), and the tetravalent group represented by the formula (4) to the sum of the valent groups is 80 mol % or less, and
The ratio of the divalent group including the structure represented by the formula (2) to the sum of the divalent group represented by the formula (B-1) and the divalent group including the structure represented by the formula (2) is , Polyimide precursor, characterized in that 20 mol% or more and 80 mol% or less.

(Wherein, A ₁ is a tetravalent group having an aromatic ring or an alicyclic structure, B ₁ is a divalent group having an aromatic ring or an alicyclic structure, and R ₁ and R ₂ are each independently hydrogen and having 1 to 6 carbon atoms. It is an alkyl group or an alkylsilyl group having 3 to 9 carbon atoms, provided that A ₁ and B ₁ included in each repeating unit may be the same or different.)

As a polyimide comprising a repeating unit represented by the following general formula (5),
A ₂ of the following general formula (5) contains a tetravalent group represented by the following formula (A-1), and B ₂ of the following general formula (5) is 2 represented by the following formula (B-1) including the flag of the family,
Further, B ₂ of the following general formula (5) contains a divalent group containing a structure represented by the following formula (2), and A ₂ of the following general formula (5) is represented by the following formula (2) It may include at least one selected from a tetravalent group including the structure represented by the following formula (3) and a tetravalent group represented by the following formula (4),
A tetravalent group represented by the formula (A-1) in 100 mol% of A ₂ in the general formula (5), a tetravalent group containing a structure represented by the formula (2), a tetravalent group represented by the formula (3) , and the content ratio of the sum of the tetravalent groups represented by the formula (4), the divalent group represented by the formula (B-1) in 100 mol% of B ₂ in the general formula (5), and the formula (2) The sum of the content ratio of the sum of the divalent groups including the structure shown is 120 mol% or more,
However, the tetravalent group represented by Formula (A-1), the tetravalent group containing the structure represented by Formula (2), the tetravalent group represented by Formula (3), and 4 represented by Formula (4) The ratio of the tetravalent group including the structure represented by formula (2), the tetravalent group represented by the formula (3), and the tetravalent group represented by the formula (4) to the sum of the valent groups is 80 mol % or less, and
The ratio of the divalent group including the structure represented by the formula (2) to the sum of the divalent group represented by the formula (B-1) and the divalent group including the structure represented by the formula (2) is , 20 mol% or more and 80 mol% or less of polyimide.

(Wherein, A ₂ is a tetravalent group having an aromatic ring or alicyclic structure, and B ₂ is a divalent group having an aromatic ring or alicyclic structure. However, A ₂ and B ₂ contained in each repeating unit are the same or different.)

The polyimide obtained from the polyimide precursor of Claim 1. A varnish comprising the polyimide precursor according to claim 1 or the polyimide according to claim 2 . The polyimide film obtained using the varnish containing the polyimide precursor of Claim 1, or the polyimide of Claim 2. The film containing the polyimide of Claim 2 or 3 is formed on the glass base material, The laminated body characterized by the above-mentioned. A substrate for a display, a touch panel, or a solar cell comprising the polyimide according to claim 2 or 3 .