TW201936717A - Polyimide precursor, polyimide, polyimide film, varnish and substrate - Google Patents

Abstract

Provided is a polyimide which contains a repeating unit represented by general formula (5). A2 in general formula (5) includes a tetravalent group represented by formula (A-1), B2 in general formula (5) includes a divalent group represented by formula (B-1), and A2 and/or B2 include a specific proportion of a tetravalent or divalent group containing a specific structure. This polyimide exhibits high transparency, has a low coefficient of linear thermal expansion, and has a low phase difference (retardation) in the thickness direction. (In the formula, A2 is a tetravalent group having an aromatic ring or an alicyclic structure, and B2 is a divalent group having an aromatic ring or an alicyclic structure. However, groups A2 and B2 contained in individual repeating units may be the same as, or different from, each other.).

Description

Polyimine precursor, polyimine, polyimide film, varnish and substrate

The present invention relates to a polyimide having a high transparency and a low coefficient of thermal expansion and a small retardation in the thickness direction and a precursor thereof. Further, the present invention relates to a varnish and a substrate comprising a polyimide film, a polyimide precursor or a polyimide.

In recent years, with the advent of a highly information society, development of optical materials such as liquid crystal alignment films or protective films for color filters in the field of display devices such as optical fibers or optical waveguides in the field of optical communication has progressed. In particular, in the field of display devices, plastic substrates having superior lightness and flexibility in replacing glass substrates have been explored, or development of bendable and roundable displays has been actively pursued. Therefore, optical materials of higher performance that can be used in such applications are sought.

The aromatic polyimine is inherently colored yellowish due to the formation of intramolecular conjugates or charge transport complexes. As a method for suppressing coloring, for example, a fluorine atom is introduced intramolecularly, a bending property is imparted to a main chain, and a group having a large introduction volume is used as a side chain to prevent the formation of an intramolecular conjugate or a charge transport complex. A way to demonstrate transparency.

Further, there has been proposed a method of exhibiting transparency by using a semi-alicyclic or full-alicyclic polyimine which theoretically does not form a charge transporting complex. In particular, many highly transparent semi-alicyclic polyethylenimines using an aromatic tetracarboxylic dianhydride as a tetracarboxylic acid component, an alicyclic diamine as a diamine component, and an alicyclic tetracarboxylic acid have been proposed. The acid dianhydride is a highly transparent semi-alicyclic polyimine which is a tetracarboxylic acid component and an aromatic diamine as a diamine component.

For example, Patent Document 1 discloses a polyimine which uses norbornane-2-spiro-α-cyclopentanone-α'-spiro-2''-norbornane-5,5'',6, 6''-tetracarboxylic dianhydride (abbreviation: CpODA) as a tetracarboxylic acid component, using 2,2'-bis(trifluoromethyl)benzidine (abbreviation: TFMB) or TFMB with other aromatic diamines (for example) TFMB: 4,4'-diamine benzanilide: 9,9-bis(4-aminophenyl)anthracene = 5:4:1 (mole ratio)) as a diamine component. Patent Document 2 discloses a polyimine in which CpODA having a specific stereoisomer ratio is used as a tetracarboxylic acid component, and TFMB and other aromatic diamines are used (for example, TFMB: 4,4'-diamine benzene) Formamidine = 5:5 (mole ratio), etc. as a diamine component.

Further, Patent Document 3 discloses a polyimine resin comprising a constituent unit A derived from a tetracarboxylic dianhydride and a polyimine resin derived from a constituent unit B derived from a diamine compound, wherein the constituent unit A A constituent unit derived from CpODA (A-1), a constituent unit derived from pyromellitic dianhydride (A-2), and a composition derived from 1,2,4,5-cyclohexanetetracarboxylic dianhydride At least one of the units (A-3), the constituent unit B includes a constituent unit (B-1) derived from 9,9-bis(4-aminophenyl)fluorene, and constitutes a constituent unit in the unit B (B) The ratio of -1) is 60 mol% or more. More specifically, in Example 4 of Patent Document 3, a polyimide resin was produced from CpODA (A-1) and 9,9-bis(4-aminophenyl)anthracene (B-1). In Example 5 of Patent Document 3, CpODA (A-1), 1,2,4,5-cyclohexanetetracarboxylic dianhydride (A-3) and 9,9-bis(4-amino group) Phenyl) oxime (B-1) to produce a polyimide resin ((A-1): (A-3) = 1:1 (mole ratio)). In Example 6 of Patent Document 3, CpODA(A-1), 9,9-bis(4-aminophenyl)anthracene (B-1) and 2,2'-dimethylbenzidine (B) -2) Production of a polyimide resin ((B-1): (B-2) = 4:1 (mole ratio)).

Further, in Example 1 and Comparative Example 1 of Patent Document 4, CpODA, 4,4'-diamino-2,2'-dimethylbiphenyl and 9,9-bis(4-amino group) are described. Polyphenylimine obtained from phenyl)anthracene (mole ratio: 1/1) and polyiminimide obtained from CpODA and 9,9-bis(4-aminophenyl)anthracene. [Prior Technical Literature] [Patent Literature]

[Patent Document 1] International Publication No. 2013/ 133 727 [Patent Document 2] International Publication No. 2014/046064 [Patent Document 3] International Publication No. 2017/191822 [Patent Document 4] JP-A-2017-133027

[Problems to be solved by the invention]

Depending on the application, for example, in the use of a display or the like, in addition to having high transparency and a low coefficient of thermal expansion, a polyimide and a polyimide film having a small retardation in the thickness direction are required. If the light penetrates the film having a large difference in the thickness direction, the color of the transmitted light cannot be accurately displayed, and the problem of bleeding and narrowing of the field of view may occur. Therefore, particularly in display applications and the like, it is desirable to reduce the phase difference in the thickness direction.

SUMMARY OF THE INVENTION An object of the present invention is to provide a polyimine having a high transparency and a low coefficient of thermal expansion and a small retardation in the thickness direction and a precursor thereof. [Means for solving the problem]

The present invention relates to the following items. A polyimine precursor which is a polyimine precursor comprising a repeating unit represented by the following formula (1), characterized in that: A _{1 of the} following formula (1) comprises the following formula a tetravalent group represented by (A-1), and B _{1 of the} following general formula (1) includes a divalent group represented by the following formula (B-1), and further, the following general formula (1) A ₁ and/or B ₁ includes a tetravalent or divalent group having a structure represented by the following formula (2), or A _{1 of the} following formula (1) includes 4 represented by the following formula (3) a valence group and/or a tetravalent group represented by the following formula (4), a tetravalent group represented by the formula (A-1) in A ₁ 100 mol% of the formula (1), having a formula (2) The content ratio of the tetravalent group of the structure shown, the tetravalent group represented by the formula (3), and the tetravalent group represented by the formula (4), and the formula (1) The sum of the ratios of the total amount of the divalent group represented by the formula (B-1) represented by the formula (B-1) and the divalent group having the structure represented by the formula (2) in the B ₁ 100 mol %, at 120 mol % or more, wherein the tetravalent group represented by the formula (A-1), the tetravalent group having the structure represented by the formula (2), the tetravalent group represented by the formula (3), and the formula ( 4) the total amount of the tetravalent group shown, the tetravalent group having the structure represented by the formula (2), The ratio of the tetravalent group shown in (3) to the tetravalent group represented by the formula (4) is 80 mol% or less, and the divalent group and the formula are represented by the formula (B-1). (2) The total amount of the divalent group in the structure shown, the ratio of the divalent group having the structure represented by the formula (2) is 80 mol% or less.

[Chemical 1] (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 carbon number; An alkyl group of 1 to 6 or an alkanoyl group having 3 to 9 carbon atoms, wherein A ₁ and B ₁ contained in each repeating unit may be the same or different).

[Chemical 2]

[Chemical 3]

[Chemical 4]

[Chemical 5]

[Chemical 6]

2. Polyimine, which is a polyimine comprising a repeating unit represented by the following formula (5), characterized in that A _{2 of the} following formula (5) contains the following formula (A-1) a tetravalent group shown, and B _{2 of the} following formula (5) includes a divalent group represented by the following formula (B-1), and further, A _{2 of the} following formula (5) and / or B ₂ contains a tetravalent or divalent group having a structure represented by the following formula (2), or A _{2 of the} following 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 A ₂ 100 mol% of the formula (5), having the formula (2) The content ratio of the tetravalent group of the structure, the tetravalent group represented by the formula (3), and the tetravalent group represented by the formula (4), and the B ₂ 100 mol% of the formula (5) And the sum of the content ratios of the total amount of the divalent group represented by the formula (B-1) and the divalent group having the structure represented by the formula (2) in the range of 120 mol% or more, wherein a tetravalent group represented by the formula (A-1), a tetravalent group having a structure represented by the formula (2), a tetravalent group represented by the formula (3), and a tetravalent group represented by the formula (4) a total amount of a group, a tetravalent group having a structure represented by the formula (2), a tetravalent group represented by the formula (3), and (4) The ratio of the tetravalent group shown is 80 mol% or less, and the divalent group represented by the formula (B-1) and the divalent group having the structure represented by the formula (2) The total amount of the group, the ratio of the divalent group having the structure represented by the formula (2) is 80 mol% or less.

[Chemistry 7] (In the formula, A ₂ is a tetravalent group having an aromatic ring or an alicyclic structure, and B ₂ is a divalent group having an aromatic ring or an alicyclic structure. Among them, A ₂ and B contained in each repeating unit ₂ can be the same or different).

[化8]

[Chemistry 9]

[化10]

[11]

[化12]

3. A polyimine which is obtained from the polyimine precursor of the first item. 4. A varnish comprising the polyimine precursor of the first item or the polyimine of the second item. A polyimine film obtained by using a varnish comprising the polyimine precursor of the first item or the polyimine of the second item. A laminate comprising a film comprising the second or third polyimine or a polyimine film of the fifth aspect formed on a glass substrate. 7. A substrate for a display, for a touch screen or for a solar cell, characterized by comprising the polyimine of the second or third item, or the polyimine film of the item 5. [Effects of the Invention]

According to the present invention, it is possible to provide a polyimine having a high transparency and a low coefficient of thermal expansion and a small retardation in the thickness direction and a precursor thereof.

The polyimine obtained from the polyimine precursor of the present invention and the polyimine of the present invention have high transparency and a low coefficient of thermal expansion and a small retardation in the thickness direction, so that it can be preferably used. For forming a substrate for display use or the like. Further, the polyimine obtained from the polyimine precursor of the present invention and the polyimine of the present invention can also be preferably used in forming a substrate for a touch panel for use in a solar cell.

The polyimine precursor of the present invention is a polyimine precursor comprising a repeating unit represented by the formula (1). The total content of the repeating unit represented by the formula (1) is preferably 90 mol% or more, more preferably 95 mol% or more, and particularly preferably 100 mol%, based on all the repeating units. A ₁ in the formula (1) is a tetravalent group having an aromatic ring or an alicyclic structure, and preferably a tetravalent group having an alicyclic structure. B ₁ in the formula (1) is a divalent group having an aromatic ring or an alicyclic structure, and preferably a divalent group having an aromatic ring.

Next, in the polyimine precursor of the present invention, A ₁ in the formula (1) contains a tetravalent group represented by the formula (A-1), and B ₁ in the formula (1) The divalent group represented by the formula (B-1) is further contained, and further, A ₁ and/or B _{1 of} the formula (1) includes a tetravalent or divalent group having the structure represented by the formula (2) The group, or A _{1 of} the formula (1), includes a tetravalent group represented by the formula (3) and/or a tetravalent group represented by the formula (4). It is also possible that A ₁ and/or B ₁ include a tetravalent or divalent group having a structure represented by the formula (2), and A ₁ includes a tetravalent group represented by the formula (3) and/or a tetravalent group represented by the formula (4).

In addition, among these contents, the tetravalent group represented by the formula (A-1) in the A ₁ 100 mol% of the general formula (1), and the tetravalent group having the structure represented by the formula (2) The content ratio of the group, the tetravalent group represented by the formula (3), and the total amount of the tetravalent group represented by the formula (4), and the formula (B) in the B ₁ 100 mol% of the formula (1) -1) The sum of the content ratios of the total amount of the divalent group and the divalent group having the structure represented by the formula (2) is 120 mol% or more, preferably 160 mol% or more. More preferably, it is more than 180% by mole. In the above, the tetravalent group represented by the formula (A-1) in the A ₁ of the formula (1), the tetravalent group having the structure represented by the formula (2), and the formula (3) a tetravalent group and a total amount of a tetravalent group represented by the formula (4), a tetravalent group having a structure represented by the formula (2), a tetravalent group represented by the formula (3), and a formula (4) The ratio of the tetravalent group shown is 80 mol% or less, and the divalent group represented by the formula (B-1) in B ₁ of the general formula (1) and having the formula (2) The total amount of the divalent group of the structure shown in the formula has a ratio of a divalent group having a structure represented by the formula (2) of 80 mol% or less. Further, the sum of the two ratios is preferably 125 mol% or less.

The polyimine of the present invention is a polyimine containing a repeating unit represented by the formula (5). The total content of the repeating unit represented by the formula (5) is preferably 90 mol% or more, more preferably 95 mol% or more, and particularly preferably 100 mol%, based on all the repeating units. A ₂ in the formula (5) is a tetravalent group having an aromatic ring or an alicyclic structure, and preferably a tetravalent group having an alicyclic structure. B ₂ in the formula (5) is a divalent group having an aromatic ring or an alicyclic structure, and preferably a divalent group having an aromatic ring.

Next, in the polyimine of the present invention, A ₂ in the formula (5) contains a tetravalent group represented by the formula (A-1), and B ₂ in the formula (5) contains the tetravalent group. a divalent group represented by the formula (B-1), further, A ₂ and/or B _{2 of} the formula (5) contains a tetravalent or divalent group having the structure represented by the formula (2) Or A _{2 of} the formula (5) includes a tetravalent group represented by the formula (3) and/or a tetravalent group represented by the formula (4). A ₂ and/or B ₂ , a tetravalent or divalent group having a structure represented by the formula (2), and A ₂ may further comprise a tetravalent group represented by the formula (3) and/or a tetravalent group represented by the formula (4).

Further, among these contents, a tetravalent group represented by the formula (A-1) in the A ₂ 100 mol% of the formula (5), and a tetravalent group having a structure represented by the formula (2) The content ratio of the group, the tetravalent group represented by the formula (3), and the total amount of the tetravalent group represented by the formula (4), and the formula (B) in the B ₂ 100 mol% of the formula (5) -1) The sum of the content ratios of the total amount of the divalent group and the divalent group having the structure represented by the formula (2) is 120 mol% or more, preferably 160 mol% or more. More preferably, it is more than 180% by mole. In the above, the tetravalent group represented by the formula (A-1) in the A ₂ of the formula (5), the tetravalent group having the structure represented by the formula (2), and the formula (3) a tetravalent group and a total amount of a tetravalent group represented by the formula (4), a tetravalent group having a structure represented by the formula (2), a tetravalent group represented by the formula (3), and a formula (4) The ratio of the tetravalent group shown is 80 mol% or less, and the divalent group represented by the formula (B-1) in B ₂ of the general formula (5) and having the formula (2) The total amount of the divalent group of the structure shown is such that the ratio of the divalent group having the structure represented by the formula (2) is 80 mol% or less. Further, the sum of the ratios of the two is preferably 125 mol% or less.

In the present specification, the following abbreviations are used as appropriate.

CpODA: norbornane-2-spiro-α-cyclopentanone-α'-spiro-2''-norbornane-5,5'',6,6''-tetracarboxylic dianhydride CpODA, etc. Cyclohexane-2-spiro-α-cyclopentanone-α'-spiro-2''-norbornane-5,5'',6,6''-tetracarboxylic acid, etc. (tetracarboxylic acid and the like represent tetracarboxylic acid Acid, and tetracarboxylic acid derivatives such as tetracarboxylic dianhydride, decyl tetracarboxylate, tetracarboxylic acid ester, tetracarboxylic fluorene chloride, etc.) TFMB: 2,2'-bis(trifluoromethyl)benzidine provides the The tetracarboxylic acid component of the tetravalent group represented by the formula (A-1) is CpODA or the like, and the diamine component which provides the divalent group represented by the formula (B-1) is TFMB. Polyimine obtained from CpODA or the like and 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 polyimine obtained from the polyimine precursor of the repeating unit of the formula (1), and A _{2 is a} tetravalent group represented by the formula (A-1), and B _{2 is} the formula ( The polyimine composed of the repeating unit of the above formula (5) of the divalent group represented by B-1) has high transparency and a low linear thermal expansion coefficient, but has a large retardation in the thickness direction. Propensity. When the polyimide film is used for a display or the like, as described above, the phase difference in the thickness direction is large, and the color of the transmitted light may not be correctly displayed, the bleeding may be caused, and the field of view may be narrowed. In contrast to the above content (ratio), (1) of the general formula A tetracarboxylic acid component is derived from the structure of _a general formula (5) of A ₂ and / or structure of the diamine component derived from a group of the structure, or the general formula B B formula (1) of _a general formula (5) in the _2, having introduced into the formula (2) derived from a tetracarboxylic acid component in the structure of (1 in A) of A _1, general formula (5) of _2, is introduced into the formula (3) of a tetravalent group, and / or the formula (4) shown in the tetravalent group, whereby a high transparency can be maintained At the same time as the low-line thermal expansion coefficient, the retardation in the thickness direction is reduced. As a result, a polyimine having a high transparency and a low linear thermal expansion coefficient and a small retardation in the thickness direction can be obtained.

Here, the adjacent aromatic rings in the structure represented by the formula (2) may be directly bonded or linked by an ether bond, or may be, for example, a structure represented by the following formula (2').

[Chemistry 13] (wherein R is a direct bond or an ether bond (-O-)).

Further, the aromatic ring contained in the structure represented by the formula (2) may be substituted with an alkyl group such as a methyl group or a fluorinated alkyl group such as a trifluoromethyl group or a halogen group, but usually It is preferred that it does not have a substituent. In addition, the substitution position is not particularly limited.

The tetracarboxylic acid component having a tetravalent group having a structure represented by the formula (2) is a tetracarboxylic acid or the like having the structure represented by the formula (2), and examples thereof include 9,9'-bis (3). , 4-dicarboxyphenyl)ruthenic anhydride or other derivative (tetracarboxylic acid derivative such as tetracarboxylic acid decyl ester, tetracarboxylic acid ester or tetracarboxylic cerium chloride, or tetracarboxylic acid dianhydride). A diamine component which provides a divalent group having a structure represented by the formula (2), and a diamine having a structure represented by the formula (2), for example, 9,9-bis(4-aminobenzene) ,9,9-bis(4-amino-3-chlorophenyl)anthracene, 9,9-bis(4-amino-3-fluorophenyl)anthracene, 9,9-bis(4- Amino-3-methylphenyl)anthracene, 4,4'-(spiro[茀-9,9'-呫ton]-3',6'-diylbis(oxy))diphenylamine, and the like.

Further, the tetracarboxylic acid component which provides the tetravalent group represented by the formula (3) is 1,2,4,5-cyclohexanetetracarboxylic acid or the like.

The tetracarboxylic acid component which provides the tetravalent group represented by the formula (4) is 2,3,3',4'-biphenyltetracarboxylic acid or the like.

In other words, the polyimide precursor of the present invention and the polyimine of the present invention are tetracarboxylic acids containing (a-1) CpODA or the like, (a-2) having the structure represented by the formula (2). Any one or more kinds of tetracarboxylic acid components such as 1,2,4,5-cyclohexanetetracarboxylic acid, 2,3,3',4'-biphenyltetracarboxylic acid, and (b) TFMB a diamine component or a diamine component comprising TFMB and a diamine having the structure represented by the formula (2); or (a) a tetracarboxylic acid component containing CpODA or the like and (b) comprising TFMB and having the same The diamine component of the diamine of the structure represented by the formula (2) is obtained.

As the CpODA or the like of the tetracarboxylic acid component used herein, among the six stereoisomers, trans-endo-endo-norbornane-2-spiro-α-cyclopentanone-α'- is preferably contained. Spiro-2''-norbornane-5,5'',6,6''-tetracarboxylic acid (trans-endo-endo body) and/or cis-endo-endo-norbornane-2-snail -α-cyclopentanone-α'-spiro-2''-norbornane-5,5'', 6,6''-tetracarboxylic acid, etc. (cis-endo-endo body). In one embodiment, the ratio of the trans-endo-endo body and/or the cis-endo-endo body in CpODA or the like is preferably 80 mol% or more, more preferably 90 mol% or more. It is 95% by mole or more, and particularly preferably 99% by mole or more.

The 1,2,4,5-cyclohexanetetracarboxylic acid or the like which is a tetracarboxylic acid component used herein preferably contains 1R, 2S, 4S, 5R-cyclohexane among the six stereoisomers. Alkane tetracarboxylic acids and the like. In one embodiment, the ratio of 1R, 2S, 4S, 5R-cyclohexane tetracarboxylic acid in 1,2,4,5-cyclohexanetetracarboxylic acid or the like is preferably 50% by mole or more. It is preferably more than 80% by mole, more preferably more than 90% by mole, and particularly preferably more than 95% by mole.

CpODA or the like may be used alone or in combination. Further, tetracarboxylic acid or the like having the structure represented by the formula (2), 1,2,4,5-cyclohexanetetracarboxylic acid, etc., and 2,3,3',4'-biphenyltetracarboxylic acid, etc. It can also be used alone or in combination. The diamine having the structure represented by the formula (2) may be used singly or in combination of two or more.

As the other tetracarboxylic acid component which provides the repeating unit represented by the above formula (1) or the repeating unit represented by the formula (5), any of other aromatic or alicyclic tetracarboxylic acids can be used. Although not particularly limited, for example, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane and 4-(2,5-di-tertiaryoxytetrahydrofuran-3-yl)-1 are exemplified. 2,3,4-tetrahydronaphthalene-1,2-dicarboxylic acid, pyromellitic acid, 3,3',4,4'-benzophenone tetracarboxylic acid, 3,3',4,4' -biphenyltetracarboxylic acid, 4,4'-oxydiphthalic acid, bis(3,4-dicarboxyphenyl)ruthenic anhydride, cross-linked triphenyl-3,4,3',4' -tetracarboxylic dianhydride, conjugated triphenyl-3,4,3',4'-tetracarboxylic dianhydride, biscarboxyphenyldimethyl decane, bisdicarboxyphenoxydiphenyl sulfide, sulfonium oxime Diphthalic acid, 1,2,3,4-cyclobutanetetracarboxylic acid, isopropylidenediphenoxydiphthalic acid, [1,1'-linked (cyclohexane)]- 3,3',4,4'-tetracarboxylic acid, [1,1'-linked (cyclohexane)]-2,3,3',4'-tetracarboxylic acid, [1,1'-linked ( 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'- Sulfur bis(cyclohexane-1,2-dicarboxylic acid), 4,4'-sulfonyl bis(cyclohexane-1,2-dicarboxylic acid), 4,4'-(dimethyl decane II base Bis(cyclohexane-1,2-dicarboxylic acid), 4,4'-(tetrafluoropropane-2,2-diyl)bis(cyclohexane-1,2-dicarboxylic acid), octahydrogen Pentene-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]non-7-ene-3,4 , 9,10-tetracarboxylic acid, 9-oxatricyclo[4.2.1.02,5]decane-3,4,7,8-tetracarboxylic acid, (4arH,8acH)-decahydro-1t, 4t: 5c,8c-dimethyl bridge naphthalene-2c,3c,6c,7c-tetracarboxylic acid, (4arH,8acH)-decahydro-1t,4t:5c,8c-dimethylnaphthalene-2t,3t,6c,7c a tetracarboxylic acid, a derivative of such a tetracarboxylic acid (such as tetracarboxylic dianhydride), or the like. Among these, more preferred are 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane, 4,4'-oxydiphthalic acid, 1,2,3,4-cyclobutane. Tetracarboxylic acid, (4arH, 8acH)-decahydro-1t, 4t: 5c, 8c-dimethylnaphthalene-2c, 3c, 6c, 7c-tetracarboxylic acid, (4arH, 8acH)-decahydro-1t, 4t a derivative of 5c, 8c-dimethylnaphthalene-2t, 3t, 6c, 7c-tetracarboxylic acid or the like and the acid dianhydride. These tetracarboxylic acid components may be used singly or in combination of two or more.

As the other diamine component which provides the repeating unit of the above formula (1) or the repeating unit represented by the formula (5), any of other aromatic or alicyclic diamines can be used. Although not particularly limited, for example, p-phenylenediamine, m-phenylenediamine, benzidine, 3,3'-diamino-biphenyl, 3,3'-bis(trifluoromethyl)benzidine, M-toluidine, 4,4'-diaminobenzophenone, 3,4'-diaminobenzophenone, N,N'-bis(4-aminophenyl)-p-benzoquinone Amine, N, N'-p-phenylene bis(p-aminobenzamide), 4-aminophenoxy-4-diaminobenzoate, bis(4-aminophenyl) pair Phthalate, biphenyl (4-aminophenyl)-4,4'-dicarboxylic acid, bis(p-aminobenzoic acid) p-phenylene ester, bis(4-aminophenyl) -[1,1'-biphenyl]-4,4'-dicarboxylate, [1,1'-biphenyl]-4,4'-diylbis(4-aminobenzoate), 4,4'-oxydiphenylamine, 3,4'-oxydiphenylamine, 3,3'-oxydiphenylamine, bis(4-aminophenyl)sulfide, p-methylenebis(phenylenediamine) ), 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis(4-aminophenyl)hexafluoropropane, bis(4-aminophenyl) Bismuth, 3,3-bis((aminophenoxy)phenyl)propane, 2,2-dual ( 3-amino-4-hydroxyphenyl)hexafluoropropane, bis(4-(4-aminophenoxy)diphenyl)anthracene, bis(4-(3-aminophenoxy)diphenyl碸, 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-isobutylcyclohexane, 1,4-diamino-2-second butylcyclohexane, 1,4-diamino-2-tert-butylcyclohexane, 1,2-diaminocyclohexane, 1,4-diaminocyclohexane, and the like, and derivatives thereof. Among these, more preferred are p-phenylenediamine, m-dibenzylamine, 4,4'-oxydiphenylamine, 1,4-bis(4-aminophenoxy)benzene, 4,4'- Bis(4-aminophenoxy)biphenyl and the like. These diamine components may be used singly or in combination of two or more.

The polyimine precursor of the present invention and the polyimine of the present invention may contain other repeating units in addition to the repeating unit represented by the formula (1) or the repeating unit represented by the formula (5). One or more. The tetracarboxylic acid component and the diamine component which provide other repeating means are not specifically limited, and other conventional tetracarboxylic acids and a conventional diamine can be used. Further, in the case where the combined diamine component is a diamine component which cannot provide the repeating unit represented by the formula (1) or the repeating unit represented by the formula (5), the tetracarboxylic acid of another repeating unit is provided. The component may also be exemplified by a tetracarboxylic acid component (also including CpODA or the like having the formula shown in the formula (1) or a repeating unit represented by the formula (5). Examples of tetracarboxylic acids and the like, 1,2,4,5-cyclohexanetetracarboxylic acid, etc., 2,3,3',4'-biphenyltetracarboxylic acid, etc.). Further, in the case where the combined tetracarboxylic acid component is a tetracarboxylic acid component which cannot provide the repeating unit represented by the formula (1) or the repeating unit represented by the formula (5), a diamine of another repeating unit is provided. The component may also be exemplified by a diamine component (also including TFMB or a structure having the formula (2)) of the repeating unit represented by the formula (1) or the repeating unit represented by the formula (5). amine).

In the polyimine precursor of the present invention, R ₁ and R ₂ in the formula (1) are each independently hydrogen, an alkyl group having 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms (particularly Any of methyl or ethyl) or an alkanoyl group having 3 to 9 carbon atoms (particularly preferably a trimethylsulfonyl group or a tert-butyldimethylthio group). In R ₁ and R ₂ , the type of the functional group and the introduction ratio of the functional group can be changed by a production method to be described later.

The introduction rate of the functional group is not particularly limited, and when an alkyl group or an alkyl fluorenyl group is introduced, 25% or more, preferably 50% or more, more preferably 75% or more of R ₁ and R ₂ may be an alkyl group or Alkyl fluorenyl. By making 25% or more of R ₁ and R ₂ into an alkyl group or an alkyl fluorenyl group, respectively, the storage stability of the polyimide precursor can be excellent.

The polyimine precursors of the present invention are independently classified according to the chemical structures employed by R ₁ and R ₂ , and can be classified into 1) poly-proline (R ₁ and R ₂ are hydrogen), 2) poly-proline The ester (at least a part of R ₁ and R ₂ is an alkyl group), 3) 4) polydecyl decylamine (at least a part of R ₁ and R ₂ is an alkane group). Next, the polyimine precursor of the present invention can be easily produced by the following production method for each of the classifications. However, the method for producing the polyimine precursor of the present invention is not limited to the following production method. 1) Polylysine

The polyimine precursor of the present invention has a tetracarboxylic dianhydride and a diamine component as a tetracarboxylic acid component of about the same molar amount, preferably a molar ratio of the diamine component to the tetracarboxylic acid component [ The molar number of the diamine component / the molar number of the tetracarboxylic acid component is preferably from 0.90 to 1.10, more preferably from 0.95 to 1.05, for example, at a lower temperature of 120 ° C or lower, inhibiting the imidization. At the same time, it is reacted in a solvent, whereby a polyimide composition precursor solution composition can be preferably obtained.

The method for synthesizing the polyimine precursor of the present invention is not limited, and more specifically, the diamine is dissolved in an organic solvent, and while stirring in the solution, the tetracarboxylic dianhydride is slowly added, at 0 to 120. The mixture is stirred at ° C, preferably 5 to 80 ° C for 1 to 72 hours to obtain a polyimide precursor. In order to easily increase the molecular weight of the polyimide precursor, the order of addition of the diamine and the tetracarboxylic dianhydride in the above production method is preferred. Further, from the viewpoint of reducing precipitates, the order of addition of the diamine and the tetracarboxylic dianhydride in the above production method may be preferably reversed.

Further, when the diamine component is excessive in the molar ratio of the tetracarboxylic acid component and the diamine component, a carboxylic acid derivative equivalent to an excess number of moles of the diamine component may be added as needed, and The molar ratio of the tetracarboxylic acid component to the diamine component is approximately equal to the same amount. The carboxylic acid derivative herein is preferably a tetracarboxylic acid which does not substantially increase the viscosity of the polyimide precursor solution, that is, substantially irrelevant to the molecular chain extension, or functions as a blocking agent. A tricarboxylic acid and its anhydride, a dicarboxylic acid, an anhydride thereof, and the like. 2) Polyamidomate

The tetracarboxylic dianhydride is reacted with an arbitrary alcohol to obtain a diester dicarboxylic acid, which is then reacted with a chlorinated reagent (thinylene chloride, grass chloroform, etc.) to obtain a diester dicarboxy ruthenium chloride. The diester dicarboxyfluorene chloride and the diamine are stirred for 1 to 72 hours at a temperature of from -20 to 120 ° C, preferably from -5 to 80 ° C to obtain a polyimine precursor. Further, the polyester imide precursor can be easily obtained by dehydrating and condensing the diester dicarboxylic acid and the diamine using a phosphorus-based condensing agent or a carbodiimide condensing agent.

The polyimine precursor obtained by this method may be purified by re-precipitation or the like by adding a solvent such as water or alcohol. 3) Polydecyl phthalate (indirect method)

The diamine is reacted with a guanylating agent in advance to obtain a guanidinated diamine. Purification of the thiolated diamine by distillation or the like is required. Next, the thiolated diamine is dissolved in a dehydrated solvent, and tetracarboxylic dianhydride is slowly added while stirring, and stirred at 0 to 120 ° C, preferably 5 to 80 ° C for 1 to 72 hours. , to obtain a polyimide precursor.

As the thiolating agent to be used herein, it is preferred to use a fluorenylating agent which does not contain chlorine, since it is not necessary to purify the fluorinated diamine. Examples of the thiolating agent containing no chlorine atom include N,O-bis(trimethyldecyl)trifluoroacetamide, N,O-bis(trimethyldecyl)acetamide, hexamethyl group. Dioxane. From the viewpoint of reducing the cost of the fluorine-containing atom, it is particularly preferably N,O-bis(trimethyldecyl)acetamide or hexamethyldioxane.

Further, in the thiolation reaction of the diamine, an amine-based catalyst such as pyridine, piperidine or triethylamine may be used to promote the reaction. This catalyst can be used directly as a polymerization catalyst for the polyimide precursor. 4) Poly(decyl) methacrylate (direct method)

The polyamic acid solution obtained by the method of 1) is mixed with a thiolating agent, and stirred at 0 to 120 ° C, preferably 5 to 80 ° C for 1 to 72 hours to obtain a polyimine precursor.

As the thiolating agent to be used herein, it is preferred to use a fluorenyl-free thiolating agent, since it is not necessary to purify the thiolated polyamic acid or the obtained polyimine. Examples of the thiolating agent containing no chlorine atom include N,O-bis(trimethyldecyl)trifluoroacetamide, N,O-bis(trimethyldecyl)acetamide, and hexamethyl Dioxazolidine. From the viewpoint of reducing the cost of the fluorine-containing atom, it is particularly preferably N,O-bis(trimethyldecyl)acetamide or hexamethyldioxane.

This production method can be suitably carried out in an organic solvent, and as a result, the varnish of the polyimide precursor of the present invention can be easily obtained.

The solvent used in the preparation of the polyimide precursor is preferably, for example, N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, An aprotic solvent such as 1,3-dimethyl-2-imidazolidinone or dimethylhydrazine, particularly preferably N,N-dimethylacetamide, N-methyl-2-pyrrolidone As long as the raw material monomer component and the produced polyimine are soluble, various solvents can be used without any problem, and the structure thereof is not particularly limited. As the solvent, a decylamine solvent such as N,N-dimethylformamide, N,N-dimethylacetamide or N-methylpyrrolidone, γ-butyrolactone, γ- is preferably used. a cyclic ester solvent such as valerolactone, δ-valerolactone, γ-caprolactone, ε-caprolactone, α-methyl-γ-butyrolactone, ethyl carbonate, propyl carbonate, etc. A glycol solvent such as a carbonate solvent or triethylene glycol, a phenol solvent such as m-cresol, p-cresol, 3-chlorophenol or 4-chlorophenol, acetophenone or 1,3-dimethyl-2- Imidazolidinone, cyclobutyl hydrazine, dimethyl hydrazine and the like. Further, other general organic solvents, that is, phenol, o-cresol, butyl acetate, ethyl acetate, isobutyl acetate, propylene glycol methyl acetate, ethyl cyanidin, butyl oxime may also be used. Sodium, 2-methyl cyproterone acetate, ethyl cyproterone acetate, butyl cyproterone 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, chlorobenzene, decene, Mineral concentrate, petroleum brain solvent, etc. Further, the solvent may be used in combination of a plurality of types.

In the present invention, the logarithmic viscosity of the polyimide precursor is not particularly limited, and the logarithmic viscosity in the N,N-dimethylacetamide solution having a concentration of 0.5 g/dL at 30 ° C is preferably 0.2 dL / More than g, more preferably 0.8 dL/g or more, and particularly preferably 0.9 dL/g or more. When the logarithmic viscosity is 0.2 dL/g or more, the molecular weight of the polyimide precursor is high, and the obtained polyimine has excellent mechanical strength and heat resistance.

In the present invention, the varnish of the polyimine precursor (polyimine precursor solution composition) contains at least the polyimine precursor of the present invention and a solvent, and a solvent, a tetracarboxylic acid component and a diamine component. The total amount of the tetracarboxylic acid component and the diamine component is 5% by mass or more, preferably 10% by mass or more, and more preferably 15% by mass or more. Further, it is usually 60% by mass or less, preferably 50% by mass or less. This concentration is close to the solid content concentration of the polyimide precursor. If the concentration is too low, for example, it may be difficult to control the film thickness of the polyimide film obtained when the polyimide film is produced.

The solvent used as the varnish for the polyimide precursor of the present invention is not particularly limited as long as it can dissolve the polyimide precursor. The solvent used for the varnish of the polyimide precursor may be the same as the solvent used in the preparation of the above polyimide precursor, and the solvent used in the preparation of the polyimide precursor may be directly used as the polyimide. The solvent of the varnish of the amine precursor is used. Further, the solvent or the solvent may be removed from the polyimine precursor solution prepared as described above, depending on the demand.

In the present invention, the viscosity (rotational viscosity) of the varnish of the polyimide precursor is not particularly limited, and the rotational viscosity measured at a temperature of 25 ° C and a shear rate of 20 sec ^-1 is preferably 0.01 using an E-type rotational viscometer. 1000 Pa·sec, more preferably 0.1 to 100 Pa·sec. In addition, thixotropy can be imparted in response to demand. Among the viscosities in the above range, it is easy to handle during coating and film formation, and it is possible to suppress an eye hole and to have excellent coating uniformity, so that a good coating film can be obtained.

The varnish of the polyimine precursor of the present invention may contain a chemical quinone imidating agent (an acid anhydride such as acetic anhydride or an amine compound such as pyridine or isoquinoline), an antioxidant, or a filler (cerium oxide, etc.) depending on the demand. A coupling agent such as an inorganic particle or the like, a dye, a pigment, a decane coupling agent, a primer, a flame retardant, an antifoaming agent, a smoothing agent, a rheology control agent (flow aid), a release agent, and the like.

The polyimine of the present invention can be preferably produced by performing a dehydration ring-closure reaction (oxime imidization reaction) of the polyimine precursor of the present invention as described above. The method for the imidization of hydrazine is not particularly limited, and a conventional method of thermal sulfiliation or chemical hydrazylation can be preferably applied.

The form of the obtained polyimine is preferably a film, a laminate of a polyimide film and another substrate, a coating film, a powder, a bead, a molded body, a foam, a varnish, or the like.

An example of a method for producing a polyimine film/substrate laminate or a polyimide film using the polyimide intermediate of the present invention will be described below. However, it is not limited to the following methods.

The varnish of the polyimine precursor of the present invention is cast and applied onto a substrate, and is heated at 20 to 180 ° C, preferably in an inert gas such as nitrogen or air in a vacuum, at 20 to 180 ° C. Drying is carried out at a temperature ranging from 20 to 150 °C. Next, the obtained polyimine precursor film is placed on the substrate, or in a state where the polyimide film is peeled off from the substrate and the ends of the film are fixed, in a vacuum, nitrogen In an inert gas or air, hot air or infrared rays are used, and heated at a temperature of 200 to 500 ° C, more preferably about 250 to 450 ° C, to produce a polyimide film/substrate laminate. Body or polyimine film. Further, in order to prevent oxidative degradation of the obtained polyimide film, it is desirable to carry out heating oxime imidization in a vacuum or in an inert gas. If the temperature at which the imidization is heated is not too high, it may be carried out in the air.

The substrate is not particularly limited, and for example, a substrate such as ceramic (glass, tantalum, alumina), metal (copper, aluminum, stainless steel), or heat-resistant plastic film (polyimine film) can be used. In one embodiment, a polyimide film/glass substrate laminate in which a polyimide film is formed on a glass substrate as a substrate is preferably used in the production. The substrate of the display, etc.

Further, the ruthenium imidization reaction of the polyimide precursor may be carried out by chemical treatment instead of the heat treatment by the above heat treatment in the presence of a tertiary amine such as pyridine or triethylamine. The polyimide precursor is immersed in a solution containing an anhydrocyclization reagent such as acetic anhydride or the like. Further, these dehydrated cyclization reagents are put into a varnish of a polyimide precursor in advance and stirred, cast on a substrate, and dried, whereby a partially ruminated imine imine can be produced. The precursor is further subjected to the above heat treatment to obtain a polyimide film/substrate laminate or a polyimide film.

Further, the polyimine of the present invention can be preferably produced by reacting a tetracarboxylic acid component and a diamine component in a solvent to prepare a solution composition (varnish) comprising the polyimine of the present invention. The solvent is removed from the prepared polyimine solution composition by heating or the like.

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

The tetracarboxylic acid component such as tetracarboxylic dianhydride and the diamine component are about equimolar, preferably the molar ratio of the diamine component to the tetracarboxylic acid component [molar number of diamine component / tetracarboxylic acid] The molar ratio of the acid component is preferably from 0.90 to 1.10, more preferably from 0.95 to 1.05, and the reaction is carried out in a solvent, and the composition of the polyimine solution of the present invention can be preferably obtained.

More specifically, the diamine component is dissolved in a solvent, and while stirring in the solution, a tetracarboxylic acid component such as tetracarboxylic dianhydride is slowly added, and it is preferably in the range of room temperature to 80 ° C depending on the demand. After stirring for 0.5 to 30 hours, the temperature is raised to carry out the hydrazine imidization reaction, whereby a polyimine solution can be obtained. The ruthenium imidization reaction can also be carried out by immediately raising the temperature immediately after the addition of the tetracarboxylic acid component. Further, the order of addition of the diamine component and the tetracarboxylic acid component may be reversed, and the diamine component and the tetracarboxylic acid component may be simultaneously added to the solvent.

The method of ruthenium imidization is not particularly limited, and a conventional method of thermal sulfiliation or chemical hydrazylation can be preferably applied. For example, a solution containing a tetracarboxylic acid component such as tetracarboxylic dianhydride and a diamine component is stirred at a temperature of 100 ° C or higher, preferably 120 ° C or higher, more preferably 150 to 250 ° C. The quinone imidization reaction can be carried out by reacting a tetracarboxylic acid component with a diamine component in an hour. In the case of chemical hydrazine imidation, a chemical hydrazine imidating agent (an acid anhydride such as acetic anhydride or an amine compound such as pyridine, isoquinoline or triethylamine) is added to the reaction solution to carry out a reaction. A ruthenium-based catalyst or the like may be added to the reaction solution to carry out the reaction according to the demand.

Further, the hydrazine imidization reaction can be carried out while removing the water generated during the reaction.

When the diamine component is excessive in the molar ratio of the tetracarboxylic acid component and the diamine component, a carboxylic acid derivative equivalent to an excess molar amount of the diamine component may be added in accordance with the demand, and the tetracarboxylic acid may be added. The molar ratio of the component to the diamine component is approximately the same. The carboxylic acid derivative herein is preferably a tetracarboxylic acid which does not substantially increase the viscosity of the polyimide reaction solution, that is, substantially does not substantially extend the molecular chain, or functions as a terminal blocking agent. Carboxylic acid and its anhydride, dicarboxylic acid and its anhydride, and the like.

The solvent used in the preparation of the polyimine solution is, for example, preferably N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, An aprotic solvent such as 1,3-dimethyl-2-imidazolidinone or dimethylhydrazine, particularly preferably N,N-dimethylacetamide, N-methyl-2-pyrrolidone As long as the raw material monomer component and the produced polyimine are soluble, various solvents can be used without any problem, and the structure thereof is not particularly limited. As the solvent, a decylamine solvent such as N,N-dimethylformamide, N,N-dimethylacetamide or N-methylpyrrolidone, γ-butyrolactone, γ- is preferably used. a cyclic ester solvent such as valerolactone, δ-valerolactone, γ-caprolactone, ε-caprolactone, α-methyl-γ-butyrolactone, ethyl carbonate, propyl carbonate, etc. A glycol solvent such as a carbonate solvent or triethylene glycol, a phenol solvent such as m-cresol, p-cresol, 3-chlorophenol or 4-chlorophenol, acetophenone or 1,3-dimethyl-2- Imidazolidinone, cyclobutyl hydrazine, dimethyl hydrazine and the like. Further, other general organic solvents, that is, phenol, o-cresol, butyl acetate, ethyl acetate, isobutyl acetate, propylene glycol methyl acetate, ethyl cyanidin, butyl oxime may also be used. Sodium, 2-methyl cyproterone acetate, ethyl cyproterone acetate, butyl cyproterone 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, chlorobenzene, decene, Mineral concentrate, petroleum brain solvent, etc. Further, the solvent may be used in combination of a plurality of types.

After the ruthenium imidization reaction is carried out as described above, the obtained reaction solution can be used as the composition of the polyimine solution of the present invention, either directly or by concentrating or diluting it, or even adding an additive or the like as required. Alternatively, the polyimine solution of the present invention (varnish) of the present invention can also be obtained by separating the soluble polyimine from the obtained reaction solution and then adding the isolated polyimine to the solvent. The separation of the polyimine can be carried out, for example, by dropping a reaction solution containing the obtained soluble polyimine into a poor solvent such as water or mixing it, and precipitating the polyimine (reprecipitation) ).

The polyimine solution composition of the present invention (the varnish of polyimine) contains at least the polyimine of the present invention and a solvent, and the ratio of the polyimine to the total amount of the solvent and the polyimine is 5 mass% or more, preferably 10 mass% or more, more preferably 15 mass% or more, and particularly preferably 20 mass% or more. If the concentration is too low, it is difficult to control the film thickness of the obtained polyimide film, for example, in the production of a polyimide film. Further, the polyimine is usually 60% by mass or less, preferably 50% by mass or less.

The solvent of the composition of the polyimine solution of the present invention is not particularly limited as long as it is soluble in the polyimide. The solvent used as the composition of the polyimine solution may be the same as the solvent used in the preparation of the above polyimine solution, and the solvent used in the preparation of the polyimine solution may be directly used as the composition of the polyimide reaction solution. The solvent used. Further, the solvent may be removed from the composition of the polyimine solution prepared as described above, or a solvent may be added as needed.

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

In the present invention, the viscosity (rotational viscosity) of the composition of the polyimine solution is not particularly limited, and the rotational viscosity measured at a temperature of 25 ° C and a shear rate of 20 sec ^-1 is preferably 0.01 to 1000 Pa using an E-type rotational viscometer.・sec, preferably 0.1 to 100 Pa·sec. In addition, thixotropy can be imparted in response to demand. The viscosity in the above range is easy to handle during coating and film formation, and it is possible to suppress the eye hole and the coating property, and to obtain a good coating film.

The composition of the polyimine solution of the present invention may contain an antioxidant, a filler (inorganic particles such as cerium oxide, etc.), a coupling agent such as a dye, a pigment, a decane coupling agent, a primer, a flame retardant, etc., depending on the demand. , antifoaming agent, smoothing agent, rheology control agent (flow aid), stripper, etc.

The polyimine of the present invention can be preferably obtained by removing the solvent from the polyimine solution composition prepared above. For example, the polyimide composition solution is cast and coated on a substrate, and the polyimide composition solution is heated on the substrate to remove the solvent, whereby the polyimide film/substrate laminate can be produced. The temperature of the heat treatment is not particularly limited, but is usually 80 to 500 ° C, preferably 100 to 500 ° C, more preferably about 150 to 450 ° C. The heat treatment can be carried out in a vacuum, an inert gas such as nitrogen, or in air, but it is usually desired to carry out in a vacuum or in an inert gas. Next, a polyimide film can be produced by peeling the polyimide film formed on the substrate from the substrate.

Here, the substrate is not particularly limited, and for example, a substrate such as ceramic (glass, tantalum, alumina), metal (copper, aluminum, stainless steel), or heat-resistant plastic film (polyimine film) can be used. In one embodiment, a polyimide film/glass substrate laminate in which a polyimide film is formed on a glass substrate as a substrate is preferably used in the production. A substrate for a display or the like.

Further, the composition of the polyimine solution is flow-coated, applied to a substrate, and the composition of the polyimine solution on the substrate is dried to have self-supporting properties, and the obtained auto-supporting film is further provided. The material is peeled off, and the solvent is removed by fixing the end portion of the film to remove the solvent, whereby the polyimide film can also be preferably produced. The drying conditions at the time of producing the self-supporting film can be appropriately determined. For example, the polyimide composition solution may be dried on the substrate at a temperature of about 50 to 300 °C. The temperature of the heat treatment of the self-supporting film is not particularly limited, and is usually 80 to 500 ° C, preferably 100 to 500 ° C, more preferably about 150 to 480 ° C. In this method, the heat treatment may be carried out in a vacuum or in an inert gas such as nitrogen or in air, but it is usually desired to carry out in a vacuum or in an inert gas.

Further, the form of the polyimine obtained from the composition of the polyimide reaction solution is not limited to a laminate of a film, a polyimide film and another substrate, and preferably a coating film, a powder, a bead, or a molded body. , foam, etc.

When the polyimine of the present invention thus obtained is measured by a film having a thickness of 10 μm, the coefficient of linear thermal expansion between 100 and 250 ° C is not particularly limited, and is preferably 40 ppm/K or less, more preferably 35 ppm. Below /K, more preferably 30 ppm/K or less, and particularly preferably 25 ppm/K or less. When the linear thermal expansion coefficient is large, the difference in linear thermal expansion coefficient from a conductor such as a metal becomes large, which may cause defects such as an increase in warpage when a circuit board is formed.

When the polyimide of the present invention is measured by a film having a thickness of 10 μm, the light transmittance at a wavelength of 400 nm is not particularly limited, but is preferably 80% or more, more preferably 83% or more, and particularly preferably 85. %the above. When the polyimide film is used for a display or the like, if the light transmittance is low, it is necessary to enhance the light source, and there is a problem that energy is consumed.

In the case where the polyimide of the present invention is measured by a film having a thickness of 10 μm, the haze is not particularly limited, but is preferably 2% or less, more preferably 1.5% or less, and particularly preferably 1% or less. When the polyimide film is used for a display or the like, if the haze is high, light scattering may cause image blurring.

In the case where the polyimide of the present invention is measured by a film having a thickness of 10 μm, the phase difference (R _th ) in the thickness direction is not particularly limited, but is preferably 500 nm or less, more preferably 350 nm or less, and particularly preferably 400 nm or less. . When the polyimide film is used for a display or the like, if the phase difference in the thickness direction is large, there is a possibility that the color of the transmitted light cannot be accurately displayed, bleeding, and the field of view is narrowed.

The film composed of the polyimine of the present invention is also used depending on the application, but the thickness of the film is preferably from 1 μm to 250 μm, more preferably from 1 μm to 150 μm, still more preferably from 1 μm to 100 μm, particularly preferably from 1 μm to 80 μm. In the case where a polyimide film is used for the purpose of light penetration, if the polyimide film is too thick, the light transmittance may be lowered.

The polyimine film/substrate laminate or the polyimide film obtained as described above can form a conductive layer on one surface or both sides thereof, whereby a flexible conductive substrate can be obtained.

The flexible conductive substrate can be obtained, for example, by the following method. That is, as a first method, in the polyimide film/substrate laminate, the polyimide film is not peeled off from the substrate, but is sputtered on the surface of the polyimide film by sputtering, A conductive layer of a conductive material (metal, metal oxide, conductive organic substance, conductive carbon, or the like) is formed by vapor deposition, printing, or the like to produce a conductive layer/polyimine film/substrate conductive laminate. Then, the conductive layer/polyimine film laminate is peeled off from the substrate in accordance with the demand, and a transparent and flexible conductive substrate composed of the conductive layer/polyimine film laminate can be obtained.

As a second method, the polyimide film can be peeled off from the base material of the polyimide film/substrate laminate to obtain a polyimide film having the same surface as the first method on the surface of the polyimide film. A conductive layer (a metal, a metal oxide, a conductive organic substance, or a conductive carbon) is formed to obtain a conductive layer/polyimine film laminate or a conductive layer/polyimine film/ A transparent and flexible conductive substrate composed of a conductive layered body.

Further, in the first and second methods, before the conductive layer is formed on the surface of the polyimide film, a gas such as water vapor or oxygen may be formed by sputtering, vapor deposition or gel-sol method. An inorganic layer such as a barrier layer or a light adjustment layer.

Further, the conductive layer can be preferably formed into a circuit by photolithography, various printing methods, an inkjet method, or the like.

The substrate of the present invention thus obtained has a circuit having a conductive layer interposed between the gas barrier layer or the inorganic layer on the surface of the polyimide film composed of the polyimide of the present invention. This substrate is excellent in flexibility, high transparency, bendability, heat resistance, and even has a low coefficient of thermal expansion, so that it is easy to form a precision circuit. Therefore, the substrate can be preferably used as a substrate for a display, for a touch screen, or for a solar cell.

That is, a transistor (inorganic transistor, organic transistor) is further formed on the substrate by vapor deposition, various printing methods, an inkjet method, or the like, and a flexible thin film transistor can be manufactured, and can be preferably used. A liquid crystal element, an EL element, and a photovoltaic element used for a display device.

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

Hereinafter, the present invention will be further described by way of examples and comparative examples. In addition, the invention is not limited to the following embodiments.

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

<Evaluation of Polyimine Film> [400 nm Transmittance] Using a UV-Vis spectrometer/V-650DS (manufactured by JASCO Corporation), a polyimide film having a film thickness of 10 μm and a size of 5 × 5 cm ² was measured at a wavelength of 400 nm. Transmittance.

[Haze] The haze of a polyimide film having a film thickness of 10 μm and a size of 5 × 5 cm 2 was measured in accordance with the specifications of JIS K7136 using a turbidimeter/NDH2000 (manufactured by Nippon Denshoku Industries Co., Ltd.).

[Line thermal expansion coefficient (CTE)] A polyimide film having a thickness of 10 μm was cut into a short film having a width of 4 mm to obtain a test piece, and TMA/SS6100 (manufactured by SII NanoTechnology Co., Ltd.) was used, and the distance between the chucks was 15 mm. The tensile load was 2 g, and the temperature was raised to a temperature of 20 ° C / min to 500 ° C. From the obtained TMA curve, a linear thermal expansion coefficient of 100 ° C to 250 ° C was obtained.

[Phase phase difference in phase direction (R _th )] A polyimide film having a film thickness of 10 μm and a size of 5 × 5 cm 2 was used as a test piece, and an angle of incidence was measured using an eclipse phase difference measuring device (KOBRA-WR). For 40°, the phase difference of the film was measured. From the obtained phase difference, a phase difference in the thickness direction of the film having a film thickness of 10 μm was obtained.

[Tensile modulus of elasticity, elongation at break point, stress at break point] The polyimide film was punched into a dumbbell shape of IEC-540(S) to be used as a test piece (width: 4 mm), and TENSILON manufactured by ORIENTEC Co., Ltd. was used. The initial tensile modulus, the elongation at break, and the stress at the breaking point were measured for a length of 30 mm between the chucks and a tensile speed of 2 mm/min.

The abbreviations, purity, and the like of the raw materials used in the following examples are as follows.

[Diamine component] TFMB: 2,2'-bis(trifluoromethyl)benzidine [purity: 99.83% (GC analysis)] BAFL: 9,9-bis(4-aminophenyl)anthracene 4,4 '-ODA: 4,4'-oxydiphenylamine [purity: 99.9% (GC analysis)] BAPB: 4,4'-bis(4-aminophenoxy)biphenyl SFXO: 4,4'-( Snail [茀-9,9'-呫吨]-3',6'-diylbis(oxy))diphenylamine [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 acid Anhydride [purity: 99.9% (GC analysis)] a-BPDA: 2,3,3',4'-biphenyltetracarboxylic dianhydride

[Solvent] GBL: γ-butyrolactone DMAc: N,N-dimethylacetamide

Table 1 shows the structural formulae of the tetracarboxylic acid component and the diamine component used in the examples and comparative examples.

[Table 1] [Example 1]

1.70 g (5.3 mmol) of TFMB and 7.40 g (21.3 mmol) of BAFL were added to a nitrogen-substituted reaction vessel to obtain the total mass of the monomer (the sum of the diamine component and the carboxylic acid component). 94.24 g of DMAc was added in an amount of 25 mass%, and stirred at room temperature for 1 hour. 10.20 g (26.5 mmol) of CpODA was slowly added to the solution. The mixture was stirred at 70 ° C for 3 hours and at 160 ° C for 7 hours to obtain a uniform and viscous polyimine solution. The obtained polyimide reaction solution has a hydrazine imidation ratio of 95% or more.

The polyimine solution was applied to a glass substrate, and heated under a nitrogen atmosphere (oxygen concentration of 200 ppm or less) from a room temperature to 410 ° C on a glass substrate to remove a solvent to obtain a colorless transparent polyimide film/glass laminate. body. Next, the obtained polyimine film/glass laminate was immersed in water, peeled off, and dried to obtain a polyimide film having a film thickness of 10 μm.

The properties of the polyimide film were measured, and the results are shown in Table 2-1. [Embodiment 2]

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

The polyimine solution was applied to a glass substrate, and heated under a nitrogen atmosphere (oxygen concentration of 200 ppm or less) from a room temperature to 410 ° C on a glass substrate to remove a solvent to obtain a colorless transparent polyimide film/glass laminate. body. Next, the obtained polyimine film/glass laminate was immersed in water, peeled off, and dried to obtain a polyimide film having a film thickness of 10 μm.

The properties of the polyimide film were measured, and the results are shown in Table 2-1. [Example 3]

7.00 g (21.9 mmol) of TFMB and 7.62 g (21.9 mmol) of BAFL were added to a nitrogen-substituted reaction vessel to obtain the total mass of the monomer (the sum of the diamine component and the carboxylic acid component). 94.26 g of DMAc was added in an amount of 25 mass%, and the mixture was stirred at room temperature for 1 hour. 16.80 g (43.7 mmol) of CpODA was slowly added to the solution. The mixture was stirred at 70 ° C for 3 hours and at 160 ° C for 7 hours to obtain a uniform and viscous polyimine solution. The obtained polyimide reaction solution has a hydrazine imidation ratio of 95% or more.

The polyimine solution was applied to a glass substrate, and heated under a nitrogen atmosphere (oxygen concentration of 200 ppm or less) from a room temperature to 410 ° C on a glass substrate to remove a solvent to obtain a colorless transparent polyimide film/glass laminate. body. Next, the obtained polyimine film/glass laminate was immersed in water, peeled off, and dried to obtain a polyimide film having a film thickness of 10 μm.

The properties of the polyimide film were measured, and the results are shown in Table 2-1. [Example 4]

7.00 g (21.9 mmol) of TFMB and 6.23 g (17.9 mmol) of BAFL were added to a nitrogen-substituted reaction vessel to obtain the total mass of the monomer (the sum of the diamine component and the carboxylic acid component). In an amount of 23% by mass, 95.44 g (31.81 g of DMAc and 63.63 g of GBL) of a mixed solvent of DMAc and GBL (DMAc: GBL = 1:2 (weight ratio)) was added, and the mixture was stirred at room temperature for 1 hour. 15.28 g (39.7 mmol) of CpODA was slowly added to the solution. The mixture was stirred at 70 ° C for 3 hours and at 160 ° C for 7 hours to obtain a uniform and viscous polyimine solution. The obtained polyimide reaction solution has a hydrazine imidation ratio of 95% or more.

The polyimine solution was applied to a glass substrate, and heated under a nitrogen atmosphere (oxygen concentration: 200 ppm or less) from a room temperature to 450 ° C on a glass substrate to remove a solvent to obtain a colorless transparent polyimide film/glass laminate. body. Next, the obtained polyimine film/glass laminate was immersed in water, peeled off, and dried to obtain a polyimide film having a film thickness of 10 μm.

The properties of the polyimide film were measured, and the results are shown in Table 2-1. [Example 5]

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

The polyimine solution was applied to a glass substrate, and heated under a nitrogen atmosphere (oxygen concentration: 200 ppm or less) from a room temperature to 430 ° C on a glass substrate to remove a solvent to obtain a colorless transparent polyimide film/glass laminate. body. Next, the obtained polyimine film/glass laminate was immersed in water, peeled off, and dried to obtain a polyimide film having a film thickness of 10 μm.

The properties of the polyimide film were measured, and the results are shown in Table 2-1. [Embodiment 6]

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

The polyimine solution was applied to a glass substrate, and heated under a nitrogen atmosphere (oxygen concentration of 200 ppm or less) from a room temperature to 410 ° C on a glass substrate to remove a solvent to obtain a colorless transparent polyimide film/glass laminate. body. Next, the obtained polyimine film/glass laminate was immersed in water, peeled off, and dried to obtain a polyimide film having a film thickness of 10 μm.

The properties of the polyimide film were measured, and the results are shown in Table 2-1. [Embodiment 7]

10.00 g (31.2 mmol) of TFMB and 2.72 g (7.8 mmol) of BAFL were added to a nitrogen-substituted reaction vessel to obtain the total mass of the monomer (the sum of the diamine component and the carboxylic acid component). 92.82 g of DMAc was added in an amount of 23% by mass, and the mixture was stirred at room temperature for 1 hour. 15.00 g (39.0 mmol) of CpODA was slowly added to the solution. The mixture was stirred at 70 ° C for 3 hours and at 160 ° C for 7 hours to obtain a uniform and viscous polyimine solution. The obtained polyimide reaction solution has a hydrazine imidation ratio of 95% or more.

The polyimine solution was applied to a glass substrate, and heated under a nitrogen atmosphere (oxygen concentration of 200 ppm or less) from a room temperature to 410 ° C on a glass substrate to remove a solvent to obtain a colorless transparent polyimide film/glass laminate. body. Next, the obtained polyimine film/glass laminate was immersed in water, peeled off, and dried to obtain a polyimide film having a film thickness of 10 μm.

The properties of the polyimide film were measured, and the results are shown in Table 2-1. [Embodiment 8]

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 added to the nitrogen-substituted reaction vessel to feed 95.66 g of DMAc was added to the total mass of the monomer (the total of the diamine component and the carboxylic acid component) in an amount of 23% by mass, and the mixture was stirred at room temperature for 1 hour. 16.00 g (41.6 mmol) of CpODA was slowly added to the solution. The mixture was stirred at 70 ° C for 3 hours and at 160 ° C for 7 hours to obtain a uniform and viscous polyimine solution. The obtained polyimide reaction solution has a hydrazine imidation ratio of 95% or more.

The polyimine solution was applied to a glass substrate, and heated under a nitrogen atmosphere (oxygen concentration of 200 ppm or less) from a room temperature to 410 ° C on a glass substrate to remove a solvent to obtain a colorless transparent polyimide film/glass laminate. body. Next, the obtained polyimine film/glass laminate was immersed in water, peeled off, and dried to obtain a polyimide film having a film thickness of 10 μm.

The properties of the polyimide film were measured, and the results are shown in Table 2-1. [Embodiment 9]

8.00 g (25.0 mmol) of TFMB and 4.35 g (12.5 mmol) of BAFL and 1.53 g (4.2 mmol) of BAPB were added to a nitrogen-substituted reaction vessel to feed the total mass of the monomers ( 100.07 g of DMAc was added in an amount of 23% by mass based on the total of the diamine component and the carboxylic acid component, and the mixture was stirred at room temperature for 1 hour. 16.00 g (41.6 mmol) of CpODA was slowly added to the solution. The mixture was stirred at 70 ° C for 3 hours and at 160 ° C for 7 hours to obtain a uniform and viscous polyimine solution. The obtained polyimide reaction solution has a hydrazine imidation ratio of 95% or more.

The polyimine solution was applied to a glass substrate, and heated under a nitrogen atmosphere (oxygen concentration of 200 ppm or less) from a room temperature to 410 ° C on a glass substrate to remove a solvent to obtain a colorless transparent polyimide film/glass laminate. body. Next, the obtained polyimine film/glass laminate was immersed in water, peeled off, and dried to obtain a polyimide film having a film thickness of 10 μm.

The properties of the polyimide film were measured, and the results are shown in Table 2-1. [Embodiment 10]

6.00 g (18.7 mmol) of TFMB and 8.38 g (15.3 mmol) of SFXO were added to a nitrogen-substituted reaction vessel to obtain the total mass of the monomer (the sum of the diamine component and the carboxylic acid component). To a mass of 25 mass%, 82.44 g (27.48 g of DMAc and 54.96 g of GBL) of a mixed solvent of DMAc and GBL (DMAc: GBL = 1:2 (weight ratio)) was added, and the mixture was stirred at room temperature for 1 hour. 13.09 g (34.1 mmol) of CpODA was slowly added to the solution. The mixture was stirred at 70 ° C for 3 hours and at 160 ° C for 7 hours to obtain a uniform and viscous polyimine solution. The obtained polyimide reaction solution has a hydrazine imidation ratio of 95% or more.

The polyimine solution was applied to a glass substrate, and heated under a nitrogen atmosphere (oxygen concentration of 200 ppm or less) from a room temperature to 410 ° C on a glass substrate to remove a solvent to obtain a colorless transparent polyimide film/glass laminate. body. Next, the obtained polyimine film/glass laminate was immersed in water, peeled off, and dried to obtain a polyimide film having a film thickness of 10 μm.

The properties of the polyimide film were measured, and the results are shown in Table 2-1. [Example 11]

11.00 g (34.4 mmol) of TFMB and 5.13 g (14.7 mmol) of BAFL were added to a nitrogen-substituted reaction vessel to obtain the total mass of the monomer (the sum of the diamine component and the carboxylic acid component). In an amount of 25 mass%, 87.29 g (29.10 g of DMAc and 58.19 g of GBL) of a mixed solvent of DMAc and GBL (DMAc: GBL = 1:2 (weight ratio)) was added, and the mixture was stirred at room temperature for 1 hour. 4.72 g (12.3 mmol) of CpODA and 8.25 g (36.8 mmol) of PMDA-H were slowly added to the solution. The mixture was stirred at 70 ° C for 3 hours and at 160 ° C for 7 hours to obtain a uniform and viscous polyimine solution. The obtained polyimide reaction solution has a hydrazine imidation ratio of 95% or more.

The polyimine solution was applied to a glass substrate, and heated under a nitrogen atmosphere (oxygen concentration of 200 ppm or less) from a room temperature to 410 ° C on a glass substrate to remove a solvent to obtain a colorless transparent polyimide film/glass laminate. body. Next, the obtained polyimine film/glass laminate was immersed in water, peeled off, and dried to obtain a polyimide film having a film thickness of 10 μm.

The properties of the polyimide film were measured, and the results are shown in Table 2-2. [Embodiment 12]

10.00 g (31.2 mmol) of TFMB and 4.66 g (13.4 mmol) of BAFL were added to a nitrogen-substituted reaction vessel to obtain the total mass of the monomer (the sum of the diamine component and the carboxylic acid component). In an amount of 25 mass%, 84.71 g (28.24 g of DMAc and 56.47 g of GBL) of a mixed solvent of DMAc and GBL (DMAc: GBL = 1:2 (weight ratio)) was added, and the mixture was stirred at room temperature for 1 hour. 8.57 g (22.3 mmol) of CpODA and 5.00 g (22.3 mmol) of PMDA-H were slowly added to the solution. The mixture was stirred at 70 ° C for 3 hours and at 160 ° C for 7 hours to obtain a uniform and viscous polyimine solution. The obtained polyimide reaction solution has a hydrazine imidation ratio of 95% or more.

The polyimine solution was applied to a glass substrate, and heated under a nitrogen atmosphere (oxygen concentration of 200 ppm or less) from a room temperature to 410 ° C on a glass substrate to remove a solvent to obtain a colorless transparent polyimide film/glass laminate. body. Next, the obtained polyimine film/glass laminate was immersed in water, peeled off, and dried to obtain a polyimide film having a film thickness of 10 μm.

The properties of the polyimide film were measured, and the results are shown in Table 2-2. [Example 13]

10.00 g (31.2 mmol) of TFMB and 4.66 g (13.4 mmol) of BAFL were added to a nitrogen-substituted reaction vessel to obtain the total mass of the monomer (the sum of the diamine component and the carboxylic acid component). In an amount of 25 mass%, 90.06 g (30.02 g of DMAc and 60.04 g of GBL) of a mixed solvent of DMAc and GBL (DMAc: GBL = 1:2 (weight ratio)) was added, and the mixture was stirred at room temperature for 1 hour. 12.86 g (33.5 mmol) of CpODA and 2.50 g (11.1 mmol) of PMDA-H were slowly added to the solution. The mixture was stirred at 70 ° C for 3 hours and at 160 ° C for 7 hours to obtain a uniform and viscous polyimine solution. The obtained polyimide reaction solution has a hydrazine imidation ratio of 95% or more.

The polyimine solution was applied to a glass substrate, and heated under a nitrogen atmosphere (oxygen concentration of 200 ppm or less) from a room temperature to 410 ° C on a glass substrate to remove a solvent to obtain a colorless transparent polyimide film/glass laminate. body. Next, the obtained polyimine film/glass laminate was immersed in water, peeled off, and dried to obtain a polyimide film having a film thickness of 10 μm.

The properties of the polyimide film were measured, and the results are shown in Table 2-2. [Embodiment 14]

7.50 g (23.4 mmol) of TFMB and 8.16 g (23.4 mmol) of BAFL were added to a nitrogen-substituted reaction vessel to obtain the total mass of the monomer (the sum of the diamine component and the carboxylic acid component). In an amount of 25 mass%, 95.40 g (31.80 g of DMAc and 63.60 g of GBL) of a mixed solvent of DMAc and GBL (DMAc: GBL = 1:2 (weight ratio)) was added, and the mixture was stirred at room temperature for 1 hour. 13.50 g (35.1 mmol) of CpODA and 2.63 g (11.7 mmol) of PMDA-H were slowly added to the solution. The mixture was stirred at 70 ° C for 3 hours and at 160 ° C for 7 hours to obtain a uniform and viscous polyimine solution. The obtained polyimide reaction solution has a hydrazine imidation ratio of 95% or more.

The polyimine solution was applied to a glass substrate, and heated under a nitrogen atmosphere (oxygen concentration of 200 ppm or less) from a room temperature to 410 ° C on a glass substrate to remove a solvent to obtain a colorless transparent polyimide film/glass laminate. body. Next, the obtained polyimine film/glass laminate was immersed in water, peeled off, and dried to obtain a polyimide film having a film thickness of 10 μm.

The properties of the polyimide film were measured, and the results are shown in Table 2-2. [Example 15]

8.00 g (25.0 mmol) of TFMB and 8.70 g (25.0 mmol) of BAFL were added to a nitrogen-substituted reaction vessel to obtain the total mass of the monomer (the sum of the diamine component and the carboxylic acid component). In an amount of 25 mass%, 95.73 g (31.91 g of DMAc and 63.82 g of GBL) of a mixed solvent of DMAc and GBL (DMAc: GBL = 1:2 (weight ratio)) was added, and the mixture was stirred at room temperature for 1 hour. 13.50 g (25.0 mmol) of CpODA and 2.63 g (25.0 mmol) of PMDA-H were slowly added to the solution. The mixture was stirred at 70 ° C for 3 hours and at 160 ° C for 7 hours to obtain a uniform and viscous polyimine solution. The obtained polyimide reaction solution has a hydrazine imidation ratio of 95% or more.

The polyimine solution was applied to a glass substrate, and heated under a nitrogen atmosphere (oxygen concentration of 200 ppm or less) from a room temperature to 410 ° C on a glass substrate to remove a solvent to obtain a colorless transparent polyimide film/glass laminate. body. Next, the obtained polyimine film/glass laminate was immersed in water, peeled off, and dried to obtain a polyimide film having a film thickness of 10 μm.

The properties of the polyimide film were measured, and the results are shown in Table 2-2. [Example 16]

15.00 g (46.8 mmol) of TFMB was added to a nitrogen-substituted reaction vessel, and 90.00 g (30.00 g) was added in an amount of 25% by mass based on the total mass of the monomer (the sum of the diamine component and the carboxylic acid component). The DMAc was mixed with 60.00 g of GBL) DMAc and GBL (DMAc: GBL = 1:2 (weight ratio)), and stirred at room temperature for 1 hour. 10.80 g (28.1 mmol) of CpODA and 4.20 g (18.7 mmol) of PMDA-H were slowly added to the solution. The mixture was stirred at 70 ° C for 3 hours and at 160 ° C for 7 hours to obtain a uniform and viscous polyimine solution. The obtained polyimide reaction solution has a hydrazine imidation ratio of 95% or more.

The polyimine solution was applied to a glass substrate, and heated under a nitrogen atmosphere (oxygen concentration: 200 ppm or less) from a room temperature to 370 ° C directly on a glass substrate to remove a solvent to obtain a colorless transparent polyimide film/glass laminate. body. Next, the obtained polyimine film/glass laminate was immersed in water, peeled off, and dried to obtain a polyimide film having a film thickness of 10 μm.

The properties of the polyimide film were measured, and the results are shown in Table 2-2. [Example 17]

15.00 g (46.8 mmol) of TFMB was added to a nitrogen-substituted reaction vessel, and 93.95 g (31.32) was added in an amount of 25% by mass based on the total mass of the monomer (diamine component and carboxylic acid component). DMAc and 62.63 g of GBL) a mixed solvent of DMAc and GBL (DMAc: GBL = 1:2 (weight ratio)), and stirred at room temperature for 1 hour. 10.80 g (28.1 mmol) of CpODA and 5.51 g (18.7 mmol) of A-BPDA were slowly added to the solution. The mixture was stirred at 70 ° C for 3 hours and at 160 ° C for 7 hours to obtain a uniform and viscous polyimine solution. The obtained polyimide reaction solution has a hydrazine imidation ratio of 95% or more.

The polyimine solution was applied to a glass substrate, and heated under a nitrogen atmosphere (oxygen concentration of 200 ppm or less) from a room temperature to 410 ° C on a glass substrate to remove a solvent to obtain a colorless transparent polyimide film/glass laminate. body. Next, the obtained polyimine film/glass laminate was immersed in water, peeled off, and dried to obtain a polyimide film having a film thickness of 10 μm.

The properties of the polyimide film were measured, and the results are shown in Table 2-2. [Comparative Example 1]

40.00 g (124.9 mmol) of TFMB was added to a nitrogen-substituted reaction vessel, and 264.04 g (88.01 g) was added in an amount of 25% by mass based on the total mass of the monomer (diamine component and carboxylic acid component). DMAc and 176.03 g of GBL) mixed solvent of DMAc and GBL (DMAc: GBL = 1:2 (weight ratio)), and stirred at room temperature for 1 hour. 48.01 g (124.9 mmol) of CpODA was slowly added to the solution. The mixture was stirred at 70 ° C for 3 hours and at 160 ° C for 7 hours to obtain a uniform and viscous polyimine solution. The obtained polyimide reaction solution has a hydrazine imidation ratio of 95% or more.

The polyimine solution was applied to a glass substrate, and heated under a nitrogen atmosphere (oxygen concentration of 200 ppm or less) from a room temperature to 410 ° C on a glass substrate to remove a solvent to obtain a colorless transparent polyimide film/glass laminate. body. Next, the obtained polyimine film/glass laminate was immersed in water, peeled off, and dried to obtain a polyimide film having a film thickness of 10 μm.

The properties of the polyimide film were measured, and the results are shown in Table 2-2.

[table 2-1]

[Table 2-2] [Industrial availability]

According to the present invention, it is possible to provide a polyimine having a high transparency and a low coefficient of thermal expansion and a small retardation in the thickness direction and a precursor thereof. The polyimine obtained from the polyimine precursor of the present invention and the polyimine of the present invention have high transparency and a low coefficient of linear thermal expansion, are easy to form a precise circuit, and have a small retardation in the thickness direction. Therefore, it is particularly suitable for use in forming a substrate for display use or the like.

no

Claims (7)

A polyimine precursor which is a polyimine precursor comprising a repeating unit represented by the following formula (1), characterized in that: A _{1 of the} following formula (1) comprises the following formula (A) -1) a tetravalent group shown, and B _{1 of the} following formula (1) contains a divalent group represented by the following formula (B-1), and further, A of the following formula (1) ₁ and/or B ₁ includes a tetravalent or divalent group having a structure represented by the following formula (2), or A _{1 of the} following formula (1) includes a tetravalent group 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) among A ₁ 100 mol% of the general formula (1), having a formula ( 2) the content ratio of the tetravalent group of the structure shown, the tetravalent group represented by the formula (3), and the tetravalent group represented by the formula (4), and the ratio of the total amount of the tetravalent group represented by the formula (4) The sum of the content ratios of the total amount of the divalent group represented by the formula (B-1) represented by the formula (B-1) and the divalent group having the structure represented by the formula (2) in B ₁ 100 mol%, at 120 mol % or more, wherein the tetravalent group represented by the formula (A-1), the tetravalent group having the structure represented by the formula (2), the tetravalent group represented by the formula (3), and the formula ( 4) the total amount of the tetravalent group shown, a tetravalent group having a structure represented by the formula (2) The ratio of the tetravalent group represented by the formula (3) to the tetravalent group represented by the formula (4) is 80 mol% or less, and has a divalent group represented by the formula (B-1) and The total amount of the divalent group of the structure represented by the formula (2), the ratio of the divalent group having the structure represented by the formula (2) is 80 mol% or less; [Chemical Formula 1] (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 carbon number; An alkyl group of 1 to 6 or an alkanoyl group having 3 to 9 carbon atoms; wherein A ₁ and B ₁ contained in each repeating unit may be the same or different); [Chemical 2] [Chemical 3] [Chemical 4] [Chemical 5] [Chemical 6] . A polyimine which is a polyimine comprising a repeating unit represented by the following formula (5), wherein: A _{2 of the} following formula (5) comprises the following formula (A-1) a tetravalent group of the formula (5), wherein the B ₂ group of the following formula (5) comprises a divalent group represented by the following formula (B-1); further, A ₂ and/or of the following formula (5) B ₂ contains a tetravalent or divalent group having a structure represented by the following formula (2), or A _{2 of the} following 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) among A ₂ 100 mol% of the general formula (5), having the formula (2) The content ratio of the tetravalent group of the structure, the tetravalent group represented by the formula (3), and the tetravalent group represented by the formula (4), and the B ₂ 100 in the formula (5) The sum of the content ratios of the total amount of the divalent group represented by the formula (B-1) and the divalent group having the structure represented by the formula (2) in the ear % is 120 mol% or more, wherein And a tetravalent group represented by the formula (A-1), a tetravalent group having a structure represented by the formula (2), a tetravalent group represented by the formula (3), and the formula (4) The total amount of the tetravalent group, the tetravalent group having the structure represented by the formula (2), and the formula 4 (4) The ratio of the group and the tetravalent group represented by the formula (4) is 80 mol% or less, and is relative to the divalent group represented by the formula (B-1) and the structure represented by the formula (2) The total amount of the divalent group, the ratio of the divalent group having the structure represented by the formula (2) is 80 mol% or less; [Chemical 7] (wherein A ₂ is a tetravalent group having an aromatic ring or an alicyclic structure, and B ₂ is a divalent group having an aromatic ring or an alicyclic structure; wherein A ₂ and B are contained in each repeating unit; ₂ can be the same or different); [Chemistry 8] [Chemistry 9] [化10] [11] [化12] . A polyimine which is obtained from a polyimide precursor as claimed in claim 1 of the patent application. A varnish comprising the polyimine precursor as claimed in claim 1 or the polyimine as in claim 2 of the patent application. A polyimine film obtained by using a varnish containing a polyimine precursor as in the first aspect of the patent application or a polyimide of the second aspect of the patent application. A laminate comprising a film comprising a polyimine according to claim 2 or 3 of the patent application or a polyimide film according to item 5 of the patent application. A substrate for a display, for a touch screen or for a solar cell, characterized by comprising the polyimine of claim 2 or 3 or the polyimine of claim 5 membrane.