JP6540382B2 - Composition containing polyimide precursor and / or polyimide, and polyimide film - Google Patents

Description

  The present invention relates to a polyimide precursor and / or a polyimide composition having a specific partial structure, a polyimide precursor composition for suppressing film whitening when forming a film, a specific partial structure, heat resistance, The present invention relates to polyimides and polyimide films excellent in transmittance, low linear expansion coefficient and low retardation.

  In recent years, in the fields of electricity, electronic components, transportation equipment, space, aircraft, etc., thinning and weight reduction of devices, and further flexibility have come to be required. In these devices, electronic elements such as thin transistors and transparent electrodes are formed on a glass substrate. By changing this glass substrate to a plastic material, the panel itself can be made flexible, thin, and lightweight. Be

In the manufacturing process of such a device, since there is a process of becoming high temperature, high heat resistance is required for the device substrate. Therefore, development of polyimide materials has been conducted as one of high heat resistance plastics. In addition, if the dimensional change in the heating process or the like is large, the device substrate may cause breakage, deformation or the like of members such as the electronic element and the color filter, and the quality stability may be deteriorated.
In addition to heat resistance, development of polyimide materials having excellent electrical insulation, abrasion resistance, chemical resistance, mechanical properties and the like has been conducted.

  In Patent Document 1, a polyimide material having heat resistance and having a small dimensional change (small linear expansion coefficient) is mentioned. Patent Document 2 proposes an amidoimide material having an amide bond.

Japan JP 2012-144603 Japanese Patent Application Laid-Open No. 2013-028688

However, as proposed in Patent Document 1, when the monomer constituting the polyimide is only an aromatic compound, the in-plane orientation becomes strong, the retardation is high, and a retardation is generated. When a material that causes such a phase difference is used, for example, the viewability in the front of the display or in the oblique direction tends to be deteriorated.
In the case of having an amide bond as in the amidimide material proposed in Patent Document 2, the amide bond tends to increase the hydrolyzability of the resulting polyimide resin because it has high water absorption and high solvent affinity. .
As described above, no material has been proposed which simultaneously satisfies the heat resistance, the transmittance, the low linear expansion coefficient, and the low retardation, which are properties necessary for application to device materials.

  The present invention has been accomplished in view of the above-mentioned problems, and an object thereof is to provide a polyimide material excellent in heat resistance, transmittance, low linear expansion coefficient and low retardation.

The present invention has the following configuration.
[1] A polyimide film containing a tetracarboxylic acid residue and a diamine residue, wherein at least one of the tetracarboxylic acid residue and the diamine residue has a bending site, and the linear expansion coefficient is 60 ppm / K or less And a retardation of 200 nm or less.
[2] The polyimide film according to the above [1], which has a yellow index of −10 or more and 20 or less when the film thickness of the film is 10 μm.
[3] A composition containing at least one of a polyimide precursor and a polyimide, wherein the polyimide precursor and the polyimide contain a tetracarboxylic acid residue and a diamine residue, and the tetracarboxylic acid residue has the following formula The partial structure represented by (1 ′), the partial structure represented by the following formula (2), and the partial structure represented by the following formula (4 ′), and the diamine residue is represented by the following formula (5) A composition having the partial structure represented, and further, at least one of the tetracarboxylic acid residue and the diamine residue has a bending site.

However, symbols in the formula have the following meanings.
X ² is a direct bond, a bond having a secondary or tertiary carbon atom, or an ether bond.
R ³ and R ⁴ are each independently a functional group selected from the group consisting of an alkyl group, an alkoxy group, an amino group and a hydroxyl group.

[4] The above-mentioned [3], wherein the proportion of the tetracarboxylic acid residue having a partial structure represented by the formula (4 ′) in the tetracarboxylic acid residue is 2 mol% or more and 95 mol% or less Composition of
[5] A tetracarboxylic acid residue having a partial structure represented by the formula (1 ′) in the tetracarboxylic acid residue and a tetracarboxylic acid residue having a partial structure represented by the formula (2) The composition according to the above [3] or [4], wherein the proportion of the addition is 5 mol% or more and 95 mol% or less.
[6] The method according to any one of the above [3] to [5], wherein the ratio of the bending site to the sum of the tetracarboxylic acid residue and the diamine residue is 0.1 mol% or more and 150 mol% or less. Composition of

  According to the present invention, it is possible to provide a polyimide precursor and / or a polyimide composition, a polyimide and a polyimide film which are excellent in heat resistance, transmittance, low linear expansion coefficient and low retardation.

The embodiments of the present invention will be described in detail below, but the objects, methods, etc. exemplified below are an example (representative example) of the embodiments of the present invention, and the present invention does not deviate from the gist of the present invention, It is not limited to these contents.
Here, "weight%" and "mass%" are synonymous.

[Composition]
The composition of the present invention is a composition comprising at least one of a polyimide precursor and a polyimide, wherein the polyimide precursor and / or the polyimide comprises a tetracarboxylic acid residue and a diamine residue, and the tetracarboxylic acid The acid residue has a partial structure selected from one or more from group I shown below and a partial structure selected from one or more from group II shown below, and the diamine residue is represented by the following formula (5) It is a composition characterized by having a partial structure represented by

However, symbols in the formula have the following meanings.
X represents a direct bond, an alkylene group, a carbonyl group, an ether bond or a sulfonyl group.
n and m each independently represent 0 or 1;
R ¹ and R ² each independently represent an alkylene group, an alkenylene group or an aromatic ring. R ¹ and R ² may be bonded to each other to form a ring.
Y represents a direct bond or a divalent organic group.
R ³ and R ⁴ each independently represent an alkyl group, an alkoxy group, an amino group or a hydroxyl group.

The tetracarboxylic acid residue has a partial structure selected from one or more from group I and a partial structure selected from one or more from group II, and a partial structure represented by formula (5) as a diamine residue By having it, the following is estimated as a reason which produces the effect of this invention.
By having a tetracarboxylic acid residue selected from Group I and a diamine residue represented by Formula (5), the heat resistance and the mechanical properties are improved, and the linear expansion coefficient is lowered. However, as described above, in the case of using only an aromatic ring compound, the in-plane orientation tends to be strong and the retardation tends to be high. However, by having a tetracarboxylic acid residue selected from Group II, these effects can be obtained. While obtaining, it becomes possible to control retardation. In addition, by having a tetracarboxylic acid residue selected from Group II, a higher transmittance can be obtained, and additionally, the effect of improving the low refractive index, the solubility in an organic solvent, and the flexibility of the molded body can be obtained. It is guessed.
In the present invention, the term "tetracarboxylic acid residue" refers to a tetravalent group derived from tetracarboxylic acid dianhydride. Further, in the present invention, the diamine residue represents a divalent group derived from a diamine compound or a diisocyanate compound.

In the composition according to the present invention, the partial structure selected from the group I is a partial structure represented by the following formula (1 ′) and a partial structure represented by the formula (2), and selected from the group II The partial structure is a partial structure represented by the following formula (4 ′), and the partial structure of the diamine residue is a partial structure represented by the following formula (5): It is preferable because it is easy to take, and it is more preferable that at least one of the tetracarboxylic acid residue and the diamine residue have a bending site.
Details of each partial structure and the bending site will be described later.

However, symbols in the formula have the following meanings.
X ² is a direct bond, a bond having a secondary or tertiary carbon atom, or an ether bond.
R ³ and R ⁴ are each independently a functional group selected from the group consisting of an alkyl group, an alkoxy group, an amino group and a hydroxyl group.

  The composition of the present invention may contain other components in addition to the polyimide precursor and / or the polyimide. For example, an imidization agent can be added to further increase the imidation ratio during film formation.

[Polyimide Precursor and / or Polyimide Contained in Composition]
The polyimide precursor and / or the polyimide contained in the composition according to the present invention comprises a tetracarboxylic acid residue and a diamine residue. A partial structure selected from the group I as one or more partial groups selected from the group II as the tetracarboxylic acid residue, and a partial structure represented by the formula (5) as the diamine residue It is not particularly limited as long as it has Moreover, it is preferable that these are compounds soluble in a solvent.
The composition of the present invention may have a polyimide precursor and / or a polyimide which does not have partial structures of groups I and II as tetracarboxylic acid residues. Moreover, you may have what does not have the partial structure represented by Formula (5) as a diamine residue.

In the present invention, “soluble in a solvent” means completely dissolved when the polyimide precursor and / or the polyimide is dissolved at 0.5% by mass at room temperature (25 ° C.) in the solvent constituting the composition. Say what to do.
The concentration to be completely dissolved is usually 0.5% by mass or more, preferably 1% by mass or more, and more preferably 10% by mass or more.
Examples of the solvent constituting the composition include a polyimide precursor contained in the composition of the present invention described later, a solvent used in obtaining the polyimide, a solvent used in reprecipitation, and the like.

The concentration of the polyimide precursor and / or the polyimide in the composition can be appropriately confirmed using a conventionally known method. For example, the solvent of the composition can be distilled off using a method such as vacuum drying, and the ratio can be determined from the mass ratio before and after the distillation.
When the concentration of the composition is less than 0.5% by mass, the composition can be concentrated to determine whether it is soluble in the solvent or not by using a method such as evaporation of the solvent under reduced pressure. When the concentration of the composition is high, the concentration can be made 0.5% by mass by diluting with a solvent of the composition. When the solvent of the composition is unknown, for example, amide solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone; aprotic solvents such as dimethyl sulfoxide; anisole The solvent can be diluted with an aromatic solvent such as cresol, xylene or toluene, or a glycol solvent such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether or propylene glycol monomethyl ether acetate .

Examples of tetracarboxylic acid residues include partial structures of groups I and II. The tetracarboxylic acid residue is not particularly limited as long as it has a partial structure selected from one or more from group I and a partial structure selected from one or more from group II, for example, a plurality of partial structures from group I And may have a plurality of partial structures represented by Formula (1).
In the group I, it is preferable to have the partial structure represented by the formula (1) because the effect of lowering the linear expansion coefficient is high, and the partial structure represented by the formula (1) and the table by the formula (2) It is further preferable to have both of the partial structures to be treated, since the heat resistance is improved, the mechanical characteristics are improved, and the linear expansion coefficient tends to be reduced.
Further, in the group II, it is preferable to have a partial structure represented by the formula (4) in order to improve the optical characteristics.

  Among the tetracarboxylic acid residues contained in the composition of the present invention, the ratio of the tetracarboxylic acid residue having a partial structure selected from each of Groups I and II is not particularly limited, but is usually 10 mol. % Or more, preferably 30 mol% or more, more preferably 50 mol% or more. Within this range, a polyimide precursor and / or a polyimide composition having good optical properties and a low linear expansion coefficient can be obtained.

The ratio of the tetracarboxylic acid residue having a partial structure selected from Group I to the tetracarboxylic acid residue having a portion selected from Group II is not particularly limited.
Among the tetracarboxylic acid residues contained in the composition of the present invention, the proportion occupied by the tetracarboxylic acid residue having a partial structure selected from Group I is usually 5 mol% or more, preferably 10 mol% or more, more preferably It is 15 mol% or more, usually 95 mol% or less, preferably 90 mol% or less, more preferably 85 mol% or less. By being in this range, it is possible to obtain a polyimide precursor and / or a polyimide composition having good optical properties and a low linear expansion coefficient.
The ratio of the tetracarboxylic acid residue having a partial structure selected from Group I to the tetracarboxylic acid residue having a partial structure selected from Group II is not particularly limited, but the ratio of Group II to Group I is usually It is 5 mol% or more, preferably 10 mol% or more, more preferably 15 mol% or more, and usually 500 mol% or less, preferably 300 mol% or less, more preferably 200 mol% or less, further preferably 150 mol% or less.

  Among the tetracarboxylic acid residues contained in the composition of the present invention, a tetracarboxylic acid residue having a partial structure represented by formula (1 ′), a tetracarboxylic acid having a partial structure represented by formula (2) The proportion of the sum of the residue and the tetracarboxylic acid residue having a partial structure represented by the formula (4 ′) is not particularly limited, but is usually 10 mol% or more, preferably 30 mol% or more, more preferably 50 mol% It is above. Within this range, a polyimide precursor and / or a polyimide composition having good optical properties and a low linear expansion coefficient can be obtained.

A tetracarboxylic acid residue having a partial structure represented by Formula (1 ′), a tetracarboxylic acid residue having a partial structure represented by Formula (2), and a partial structure represented by Formula (4 ′) The ratio to the tetracarboxylic acid residue is not particularly limited.
Among the tetracarboxylic acid residues contained in the composition of the present invention, a tetracarboxylic acid residue having a partial structure represented by formula (1 ′) and a tetracarboxylic acid having a partial structure represented by formula (2) The proportion of the sum occupied by the residues is usually 5 mol% or more, preferably 10 mol% or more, more preferably 15 mol% or more, and usually 95 mol% or less, preferably 90 mol% or less, more preferably 85 mol% or less. By being in this range, it is possible to obtain a polyimide precursor and / or a polyimide composition having good optical properties and a low linear expansion coefficient. In addition, in the polyimide film obtained from the composition, the absorption near 308 nm and 355 nm used for laser processing is increased, which may make it possible to cope with the laser processing.

  A tetracarboxylic acid residue having a partial structure represented by Formula (1 ′), a tetracarboxylic acid residue having a partial structure represented by Formula (2), and a partial structure represented by Formula (4 ′) The ratio to the tetracarboxylic acid residue is not particularly limited, but a tetracarboxylic acid residue having a partial structure represented by Formula (1 ′) and a tetracarboxylic acid residue having a partial structure represented by Formula (2) The ratio of the tetracarboxylic acid residue having a partial structure represented by the formula (4 ′) to the sum of groups is usually 5 mol% or more, preferably 10 mol% or more, more preferably 15 mol% or more, and usually 500 mol% or less Preferably it is 300 mol% or less, More preferably, it is 200 mol% or less, More preferably, it is 150 mol% or less. By being in this range, it is possible to obtain a polyimide precursor and / or a polyimide composition having good optical properties and a low linear expansion coefficient.

  Among the tetracarboxylic acid residues contained in the composition of the present invention, the proportion of the tetracarboxylic acid residue having a partial structure represented by the formula (4 ′) is usually 2 mol% or more, preferably 5 mol% or more More preferably, it is 8 mol% or more, usually 95 mol% or less, preferably 90 mol% or less, more preferably 85 mol% or less. By being in this range, it is possible to obtain a polyimide precursor and / or a polyimide composition having good optical properties and a low linear expansion coefficient.

  The ratio of the tetracarboxylic acid residue having the partial structure represented by Formula (2) to the tetracarboxylic acid residue having the partial structure represented by Formula (1 ′) is not particularly limited, but is usually 0.5 mol %, Preferably 1 mol% or more, more preferably 3 mol% or more, and usually 500 mol% or less, preferably 400 mol% or less, more preferably 300 mol% or less. By being in this range, it is possible to obtain a polyimide precursor and / or a polyimide composition having good optical properties and a low linear expansion coefficient.

  A tetracarboxylic acid residue having a partial structure represented by Formula (1 ′) in a tetracarboxylic acid residue having a partial structure represented by Formula (2) and a partial structure represented by Formula (2) The ratio to the sum of tetracarboxylic acid residues is not particularly limited, but is usually 1 mol% or more, preferably 3 mol% or more, more preferably 5 mol% or more, and usually 95 mol% or less, preferably 90 mol% or less, more preferably It is 85 mol% or less. By being in this range, it is possible to obtain a polyimide precursor and / or a polyimide composition having good optical properties and a low linear expansion coefficient.

The proportion of the tetracarboxylic acid residue can be determined by analyzing the composition of the raw material monomer by NMR, solid state NMR, IR or the like. Moreover, after melt | dissolving with an alkali, it can obtain | require by gas chromatography (GC), < ¹ > H-NMR, < ¹³ > C-NMR, two-dimensional NMR, mass spectrometry etc.

  The proportion of the diamine residue having the partial structure represented by the formula (5) in the diamine residue is not particularly limited, but is usually 0.1 mol% or more, preferably 1 mol% or more, more preferably 5 mol% or more More preferably, it is 7 mol% or more, more preferably 20 mol% or more, still more preferably 30 mol% or more, still more preferably 40 mol% or more, and still more preferably 50 mol% or more. There is no particular upper limit, and 100 mol% may be sufficient. A polyimide precursor and / or a polyimide composition for obtaining a polyimide having a low linear expansion coefficient by containing a diamine residue having a partial structure represented by the formula (5) occupied in the diamine residue in a specific amount or more be able to.

  The amount of the diamine compound for inducing a diamine residue is usually 0.7 mol or more, preferably 0.8 mol or more, and usually 1.3 mol or less, preferably 1.2 mol or less, per 1 mol of tetracarboxylic acid dianhydride. It is. By setting the amount of the diamine compound in this range, it is possible to obtain a polyimide precursor and / or a polyimide having an appropriate molecular weight range.

(Group I and Group II)
Group I: The following formulas (1) and (2) are shown.

[In formula (1),
X represents a direct bond, an alkylene group, a carbonyl group, an ether bond or a sulfonyl group. ]

Group II: The following formulas (3) and (4) are shown.

[In equation (3),
n and m each independently represent 0 or 1;
R ¹ and R ² each independently represent an alkylene group, an alkenylene group or an aromatic ring.
R ¹ and R ² may be different or the same and may form a ring. ]

[In formula (4),
Y represents a direct bond or a divalent organic group. ]

(Group I)
(Tetracarboxylic Acid Residue Having Partial Structure Represented by Formula (1))
In formula (1), X represents a direct bond, an alkylene group, a carbonyl group, an ether bond or a sulfonyl group. Among the above, X is preferably a direct bond, a carbonyl group or a sulfonyl group, and more preferably a direct bond, because the effect of lowering the linear expansion coefficient is high.

  The alkylene group is not particularly limited, but preferably has 1 or more carbon atoms, and more preferably 2 or more. On the other hand, 8 or less is preferable and 5 or less is still more preferable. The alkylene group may have a substituent, and examples thereof include an amino group, a hydroxyl group and a halogen atom.

  The tetracarboxylic acid residue having a partial structure represented by the formula (1) is not particularly limited, and, for example, 3,3 ′, 4,4′-biphenyltetracarboxylic acid dianhydride, 2,3,3 ′, Tetracarboxylic acid dianhydrides in which X is a direct bond such as 4′-biphenyl tetracarboxylic acid dianhydride, 2,2 ′, 3,3′-biphenyl tetracarboxylic acid dianhydride; Carboxyphenyl) methane dianhydride, bis (2,3-dicarboxyphenyl) methane dianhydride, 2,3,3 ′, 4′-tetracarboxyphenylmethane dianhydride, 2,2-bis (3,4 -Dicarboxyphenyl) propane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propane dianhydride, 2,2- (2,3,3 ', 4'-tetracarboxyphenyl) propane 2 Anhydride, 2, 2 Tetracarboxylic acid dianhydrides in which X is an alkylene group such as bis (3,4-dicarboxyphenyl) 1,1,1,3,3,3-hexafluoropropane dianhydride; 3,3 ′, 4, 4′-benzophenonetetracarboxylic acid dianhydride, 2,2 ′, 3,3′-benzophenonetetracarboxylic acid dianhydride, 2,3,3 ′, 4′-benzophenonetetracarboxylic acid dianhydride, etc. Tetracarboxylic acid dianhydride which is a carbonyl group; tetracarboxylic acid wherein X is an ether bond such as 4,4'-oxydiphthalic anhydride, 3,4'-oxydiphthalic anhydride, 3,3'-oxydiphthalic anhydride Acid dianhydride; 3,3 ′, 4,4′-diphenyl sulfone tetracarboxylic dianhydride, 2,3,3 ′, 4′-diphenyl sulfone tetracarboxylic dianhydride, 2,2 ′, 3 It includes tetracarboxylic acid residue derived from the tetracarboxylic dianhydride, such as; X such 3'-diphenylsulfone tetracarboxylic dianhydride dianhydride sulfonyl group.

  The partial structure of the tetracarboxylic acid residue represented by the formula (1) is a partial structure represented by the following formula (1 ′), which has the effect of improving heat resistance and mechanical properties, and lowering the linear expansion coefficient Is preferable because it tends to be obtained.

In the formula (1 ′), X ² is a direct bond, a bond having a secondary or tertiary carbon atom, or an ether bond, and among these, the direct bond is preferable because the mechanical properties are improved. Moreover, in the polyimide film obtained from this composition, since absorption of 308 nm and 355 nm vicinity used for laser processing increases and it becomes possible to respond to laser processing, it is preferable.
The bond having a secondary or tertiary carbon atom means that X ² is a C 1 secondary or tertiary carbon atom. The carbon atom of X ² is linked to a hydrogen atom and / or a substituent other than linking to the benzene ring in the formula (1 ′). Examples of the substituent linked to the carbon atom of X ² include a halogen atom, a cyano group, a nitro group, a sulfo group and the like.

(Tetracarboxylic Acid Residue Having Partial Structure Represented by Formula (2))
Examples of the tetracarboxylic acid dianhydride which derives a tetracarboxylic acid residue having a partial structure represented by the formula (2) include pyromellitic dianhydride.

(Group II)
(Tetracarboxylic Acid Residue Having Partial Structure Represented by Formula (3))
In Formula (3), n and m each independently represent 0 or 1. Although not particularly limited, at least one of n and m is preferably 1 from the viewpoint of the reactivity of imidization. R ¹ and R ² each independently represent an alkyl group, an alkenyl group or an aromatic ring. R ¹ and R ² may be different or the same and may form a ring. In addition, the alkyl group, the alkenyl group and the aromatic ring may have a substituent.
As an alkyl group and an alkenyl group, carbon number 1 or more is preferable each independently. On the other hand, 10 or less is preferable and 8 or less is still more preferable. By being in this range, the solubility in organic solvents tends to be high.
The aromatic ring may be either a single ring or a fused ring. Specifically, a benzene ring, a naphthalene ring, an anthracene ring and the like can be mentioned. In particular, a benzene ring is preferred because the solubility in organic solvents tends to be high.

The tetracarboxylic acid residue having a partial structure represented by the formula (3) is not particularly limited, and, for example, 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 1,2,3,4- Cyclopentane tetracarboxylic acid dianhydride, 1,2,4,5-cyclohexanetetracarboxylic acid dianhydride, 1,2,3,4-cyclohexanetetracarboxylic acid dianhydride, bicyclo [2,2,2] oct 7-ene-2,3,4,6-tetracarboxylic dianhydride, tricyclo [6,4,0,0 ^2,7] dodecane-1,8: 2,7-tetracarboxylic dianhydride, 1,2,3,4-Tetramethyl-1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 4- (2,5-dioxotetrahydrofuran-3-yl) -1,2,3,4 -Tetrahydronaphthalene-1,2-di Tetracarboxylic acid residue and the like which are derived from tetracarboxylic dianhydride such as carboxylic acid anhydride.

(Tetracarboxylic Acid Residue Having Partial Structure Represented by Formula (4))
Y represents a direct bond or a divalent organic group. The divalent organic group is not particularly limited, and examples thereof include an alkylene group, a carbonyl group, an ether bond and a sulfonyl group. Among these, Y is preferably a direct bond since the optical characteristics tend to be improved.
The said alkylene group is synonymous with the preferable range of the alkylene group of X of Formula (1), and the substituent which it may have is also synonymous.

The tetracarboxylic acid residue having a partial structure represented by the formula (4) is not particularly limited, and, for example, bicyclohexane-3,3 ', 4,4'-tetracarboxylic dianhydride, bicyclohexane-2 Tetracarboxylic acid derived from tetracarboxylic acid dianhydride such as 3,3,3 ′, 4′-tetracarboxylic acid dianhydride, bicyclohexane-2,2 ′, 3,3′-tetracarboxylic acid dianhydride Residues and the like can be mentioned.
Among these, a tetracarboxylic acid residue derived from bicyclohexane-3,3 ′, 4,4′-tetracarboxylic acid dianhydride is preferable since the optical properties tend to be improved.

  The partial structure of the tetracarboxylic acid residue represented by the formula (4) is preferably a partial structure represented by the following formula (4 ') because the optical properties are improved.

(Diamine residue)
The partial structure represented by Formula (5) is mentioned as a diamine residue.

[In Formula (5), R ³ and R ⁴ each independently represent an alkyl group, an alkoxy group, an amino group or a hydroxyl group. ]

(Diamine Residue Having Partial Structure Represented by Formula (5))
R ³ and R ⁴ each independently represent an alkyl group, an alkoxy group, an amino group or a hydroxyl group.
The alkyl group and the alkoxy group each independently preferably have 1 or more carbon atoms. On the other hand, 10 or less is preferable, 8 or less is still more preferable, and 6 or less is especially preferable. Within this range, the linear expansion coefficient tends to be low, which is preferable.
Each of the alkyl group and the alkoxy group may have a substituent. Examples of the substituent which the alkyl group may have include a halogen atom, a cyano group, a nitro group, a sulfo group and the like. Among these, a halogen atom is preferable, and a fluorine atom is particularly preferable. Within this range, the linear expansion coefficient tends to be low.
Examples of the substituent which the alkoxy group may have include an alkyl group having 1 to 6 carbon atoms, a halogen atom, a cyano group, a nitro group, a sulfo group, an allyl group and the like.
Among them, R ³ and R ⁴ are preferably an alkyl group or an alkoxy group because the optical properties and the linear expansion coefficient are improved, and an alkyl group having a halogen atom as a substituent tends to have a low linear expansion coefficient. Therefore, it is more preferable. R ³ and R ⁴ may be the same or different, but are preferably the same from the viewpoint of ease of production.

The diamine residue which has a partial structure represented by Formula (5) is not specifically limited. For example, R such as 4,4'-diamino-2,2'-dimethylbiphenyl, 4,4'-diamino-2,2'-diethylbiphenyl, 4,4'-diamino-2,2'-dipropylbiphenyl etc. Diamine compounds in which ³ and R ⁴ have an alkyl group; 4,4′-diamino-2,2′-bis (trifluoromethyl) biphenyl, 4,4′-diamino-2-methyl-2′-trifluoromethylbiphenyl Diamine compounds in which R ³ and R ^{4 each} have a halogenated alkyl group; 4,4'-diamino-2,2'-dimethoxybiphenyl, 4,4'-diamino-2,2'-diethoxybiphenyl, an amino group 2,2 ', 4,4'-tetra-aminobiphenyl, a hydroxyl group, the diamine of having ^{R 3} and ^{R 4} are alkoxy groups such as 4,4'-diamino-2,2'-dihydroxybiphenyl with Things; the diamine residue derived from a diamine compound such like.

(A tetracarboxylic acid residue other than the partial structure represented by Formula (1), Formula (2), Formula (3) and Formula (4), and Formula (1 ′), Formula (2), Formula (4) ') And tetracarboxylic acid residue having other than the partial structure represented by formula (5))
As a tetracarboxylic acid residue having other than the partial structure represented by the formula (1), the formula (2), the formula (3) and the formula (4) within the range not departing from the subject matter of the present invention, aromatics shown below Tetracarboxylic acid residues derived from tetracarboxylic acid dianhydrides such as tetracarboxylic acid dianhydride and aliphatic tetracarboxylic acid dianhydride can be used.
Further, the composition according to the present invention has a partial structure represented by Formula (1 ′), Formula (2), Formula (4 ′) and Formula (5), and a tetracarboxylic acid residue and a diamine residue When at least one of them has a bending site described later, as a tetracarboxylic acid residue having other than the partial structure represented by Formula (1 ′), Formula (2), Formula (4 ′) and Formula (5), Tetracarboxylic acid residues derived from tetracarboxylic acid dianhydrides such as aromatic tetracarboxylic acid dianhydrides and aliphatic tetracarboxylic acid dianhydrides shown below and partial structures represented by the formula (3) The tetracarboxylic acid residue which it has is mentioned.

(Aromatic tetracarboxylic acid dianhydride)
Examples of the aromatic tetracarboxylic acid dianhydride include tetracarboxylic acid dianhydride containing one aromatic ring in the molecule such as 1,2,3,4-benzenetetracarboxylic acid dianhydride; 2,2 ′, 6,6′-biphenyltetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) -1,1,1,3,3,3-hexafluoropropane dianhydride 2,2,2-bis (2,3-dicarboxyphenyl) -1,1,1,3,3,3-hexafluoropropane dianhydride, 2,2'-bis (trifluoromethyl) -4,4 ', 5,5'-biphenyltetracarboxylic acid dianhydride, 4,4'-(hexafluorotrimethylene) -diphthalic acid dianhydride, 4,4 '-(octafluorotetramethylene) -diphthalic acid dianhydride Have two or more independent aromatic rings such as 1,2,5,6-naphthalenedicarboxylic acid dianhydride, 1,4,5,8-naphthalenedicarboxylic acid dianhydride, 2,3,6,7-naphthalenedicarboxylic acid dianhydride , 3,4,9,10-Perylenetetracarboxylic dianhydride, 2,3,6,7-anthracenetetracarboxylic dianhydride, 1,2,7,8-phenanthrenetetracarboxylic dianhydride etc And tetracarboxylic acid dianhydrides having a fused aromatic ring of

(Aliphatic tetracarboxylic acid dianhydride)
Examples of aliphatic tetracarboxylic acid dianhydrides include alicyclic tetracarboxylic acids such as 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic acid anhydride. Dianhydrides; linear aliphatic tetracarboxylic acid dianhydrides such as ethylene tetracarboxylic acid dianhydride, butanetetracarboxylic acid dianhydride, meso-butane-1,2,3,4-tetracarboxylic acid dianhydride And the like.

(Diamine residue having other than the partial structure represented by formula (5))
The diamine residue derived from the diamine compound shown below can be used as a diamine residue which has except the partial structure represented by Formula (5) in the range which does not deviate from the main point of this invention.

  As another diamine compound, for example, a diamine compound in which one aromatic ring is contained in the molecule such as 1,4-phenylenediamine, 1,2-phenylenediamine, 1,3-phenylenediamine, etc .; -Diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 2,2-bis (4- (4-amino) Phenoxy) phenyl) propane, bis (4- (4-aminophenoxy) phenyl) sulfone, bis (4- (3-aminophenoxy) phenyl) sulfone, 1,3-bis (4-aminophenoxy) neopentane, bis (4 -Amino-3-carboxyphenyl) methane, 4,4'-diaminodiphenyl sulfone, 4,4'-dia No-diphenyl sulfide, N- (4-aminophenoxy) -4-aminobenzamine, 2,2'-bis (trifluoromethyl) -4,4'-diaminobiphenyl, bis (3-aminophenyl) sulfone, norbornane diamine 4,4'-Diamino-2- (trifluoromethyl) diphenyl ether, 5-trifluoromethyl-1,3-benzenediamine, 2,2-bis (4- (4-aminophenoxy) phenyl) hexafluoropropane, 4,4'-Diamino-2,2'-bis (trifluoromethyl) biphenyl, 2,2-bis [4- {4-amino-2- (trifluoromethyl) phenoxy} phenyl] hexafluoropropane, 2- Trifluoromethyl-p-phenylenediamine, 2,2-bis (3-amino-4-methylphenyl) phenyl Diamine compounds having two or more independent aromatic rings such as subfluoropropane and bis (4-aminophenyl) acetylene; 4,4 ′-(9-fluorenylidene) dianiline, 2,7-diaminofluorene, 1,5- And diamine compounds having a condensed aromatic ring such as diaminonaphthalene and 3,7-diamino-2,8-dimethyldibenzothiophene 5,5-dioxide.

  Among the diamine residues having other than the partial structure represented by the formula (5), it is preferable to have the diamine residue having the partial structure represented by the formula (6) in order to improve the optical properties.

[In formula (6),
Z represents a direct bond, a sulfonyl group, an alkylene group, a carbonyl group or an ether bond, and A and B each independently represent a direct bond, a divalent aromatic ring, a divalent heterocyclic ring or a phenyl ether group. ]

Among Z, in order to further improve optical properties, a sulfonyl group, an ether bond or a carbonyl group is preferable, and a sulfonyl group is more preferable.
The alkylene group for Z is not particularly limited, but preferably has 1 or more carbon atoms, and more preferably 2 or more. On the other hand, 8 or less is preferable and 5 or less is still more preferable.

A and B each independently represent a direct bond, a divalent aromatic ring, a divalent heterocycle or a phenyl ether group. The divalent aromatic ring and the divalent heterocyclic ring may have a substituent.
Among these, a phenyl ether group is preferable because the solubility in a solvent tends to be high. A and B may be the same or different, but are preferably the same from the viewpoint of ease of production.

  Specifically as a bivalent aromatic ring of A and B, a benzene ring, a naphthalene ring, an anthracene ring etc. are mentioned. Among these, a benzene ring is preferable because the solubility in a solvent tends to be high. Specific examples of the divalent heterocyclic ring of A and B include furan, thiophene, pyrrole, imidazole, pyridine, pyrimidine, pyrazine, oxazole, benzimidazole, benzoxazole and the like.

  As a diamine residue having a partial structure represented by the formula (6), for example, 4,4′-bis (4-aminophenoxy) biphenyl, 4,4′-bis (3-aminophenoxy) biphenyl, 3,3 Diamine compounds in which Z is a direct bond such as' -bis (4-aminophenoxy) biphenyl, 3,4'-bis (4-aminophenoxy) biphenyl; 3,3'-diaminodiphenyl sulfone, 4,4'-diamino Diphenyl sulfone, 3,4′-diaminodiphenyl sulfone, 2,3′-diaminodiphenyl sulfone, 2,4′-diaminodiphenyl sulfone, bis (4- (4-aminophenoxy) phenyl) sulfone, bis (4- (3 A diamine compound wherein Z is a sulfonyl group such as -aminophenoxy) phenyl) sulfone; 2,2-bis (4- (4-amino) Phenoxy) phenyl) propane, 2,2-bis (4- (3-aminophenoxy) phenyl) propane, 1,3-bis (4-aminophenoxy) neopentane, bis (4-amino-3-carboxyphenyl) methane and the like Diamine compounds in which Z is an alkylene group; 4,4′-diaminodiphenyl ketone, 3,4′-diaminodiphenyl ketone, 2,3′-diaminodiphenyl ketone, 2,4′-diaminodiphenyl ketone, etc. Diamine compounds which are groups; 3,3 ', 4,4'-tetraaminodiphenyl ketone, 4,4'-bis (4-aminophenoxy) benzophenone, 4,4'-bis (3-aminophenoxy) benzophenone and the like Diamine residues derived from diamine compounds such as diamine compounds wherein Z is an ether bond; It is.

(A tetracarboxylic acid residue and / or a diamine residue having a bending site)
In the polyimide precursor and / or the polyimide in the composition of the present invention, it is preferable to have a tetracarboxylic acid residue and / or a diamine residue having a bending site, since this tends to improve the optical properties.
In the present invention, the inflection point is an inflection point in which deformation is suppressed, and the bond angle of the ring centering on the inflection point, the surface angle of the ring bound to the inflection point, tetracarboxylic acid residue such as rotation, vibration And / or those which inhibit the movement of molecules containing diamine residues. Among them, ones which suppress the bonding angle of the ring centering on the bending site and the movement of rotation are preferable.

That is, the bent portion is preferably a trivalent or higher group which is directly bonded to the cyclic structure and the cyclic structure and the bond angle between the cyclic structures is less than 180 degrees, preferably 160 degrees or less, more preferably 130 degrees It is below. There is no particular lower limit, but it is usually 90 degrees or more.
The angle can be determined by a conventionally known calculation method. For example, empirical molecular orbital methods such as Huckel method, extended Huckel method, Hartree-Fock method, substitutional interaction method, non-empirical molecular orbital method such as multiconfiguration SCF method, PPP approximation, CNDO / 2, INDO, MNDO And semi-empirical molecular orbital methods such as AM1 and PM3, molecular dynamics methods such as MM2, and density functional methods such as BLYP and B3LYP.

In the present invention, by having the bending portion, thermal vibration of the entire polyimide precursor and / or polyimide chain is suppressed, and the coefficient of linear expansion tends to be improved. Furthermore, suppression of the interaction between the polyimide precursor and / or the polyimide chain tends to improve the optical properties such as the transmittance and YI, and the regular orientation of the same chain is disturbed, The retardation tends to improve.
In addition, the entanglement of the polyimide precursor and / or the molecular chain of the polyimide is increased, and the amount of aromatic rings in the same chain is increased, whereby the heat resistance tends to be improved.

  The polyimide precursor and / or the polyimide in the composition of the present invention usually has both a tetracarboxylic acid residue and a diamine residue having a bending site, and has a bending site, a tetracarboxylic acid It may have a residue or a diamine residue. Among these, it is preferable that the diamine residue has a bending site, since the optical properties tend to be improved. Moreover, it is also preferable that the tetracarboxylic acid residue and the diamine residue have a bending site, since the optical characteristics tend to be improved.

In the present invention, a plurality of bending sites may be provided in the tetracarboxylic acid residue and / or diamine residue bending site, but it is preferable that the plurality of bending sites are not linked. It is in the tendency to be able to maintain and improve the polymerizability because the bending sites are not connected.
In the present invention, it is preferable that a ring structure be directly bonded to the inflection point. The direct bonding of the ring structure further suppresses deformation such as the bonding angle, the surface angle of the ring bonded to the bending site, rotation, and vibration. The cyclic structure directly bonded to the inflection point may be derived from the same tetracarboxylic acid residue / diamine residue as the inflection point or may be different. In the case of being derived from the same tetracarboxylic acid residue / diamine residue as the bending site, the cyclic structure is the structure possessed by the tetracarboxylic acid monomer / diamine monomer. When not derived from the same tetracarboxylic acid residue / diamine residue as the bending site, the cyclic structure is a cyclic imide structure.

The tetracarboxylic acid residue having a bending site may be a tetracarboxylic acid residue having a partial structure represented by the above formulas (1), (2), (3) and (4), It may be a tetracarboxylic acid residue having other than the partial structure represented by Formula (1), Formula (2), Formula (3) and Formula (4).
Preferably, the tetracarboxylic acid residue having a bending site is represented by the formula (1), the formula (2), the formula (3) and the formula (4) from the viewpoint of coexistence of low linear expansion coefficient and low retardation. It is a tetracarboxylic acid residue having other than a partial structure. Furthermore, from the point of coexistence of low linear expansion coefficient and low retardation, the tetracarboxylic acid residue having a bending site is other than the partial structure represented by the above formulas (1 ′), (2) and (4 ′) It is a tetracarboxylic acid residue having
Moreover, you may have multiple tetracarboxylic-acid residues which have a bending part.
The diamine residue which has a bending part is except the partial structure represented by the said Formula (5), and may have it.

  The content of the inflection site is not particularly limited, but is usually 0.1 mol% or more, preferably 0.5 mol%, more preferably 1 mol% in proportion to the sum of tetracarboxylic acid residue and diamine residue in the composition. The above, more preferably 5 mol% or more. Also, it is usually 150 mol% or less, preferably 100 mol% or less, more preferably 50 mol% or less. By being in these ranges, the optical properties tend to be good, and the mechanical properties tend to be improved.

  As the bending site, it is preferable to have a trivalent or higher bond to the element constituting the main chain, which is bonded to the ring. Among the bonds having 3 or more valences, at least one selected from quaternary carbon atoms, hexavalent sulfur atoms, tertiary amines, and benzene rings is preferable. In particular, the optical property is improved that a tetracarboxylic acid and / or diamine residue having a bending site is one in which two or more aromatic rings are bonded by a quaternary carbon atom and / or a hexavalent sulfur atom. It is preferable because it tends to

  Those having a trivalent or higher bond are not particularly limited as long as they do not deviate from the subject matter of the present invention, and examples thereof include a structure represented by the following formula (30).

In the above formula (30), Z ¹ represents a quaternary carbon atom, a hexavalent sulfur atom, a tertiary amine or a benzene ring. Y ¹ and Y ² each independently represent a cyclic structure.
Hexafluoropropane, propane, fluorene and the like are preferable as quaternary carbons because the optical properties are improved. As hexavalent sulfur, a sulfonyl group is preferable because the optical properties are improved. As the tertiary amine, trimethylamine is preferred.

The cyclic structure of Y ¹ and Y ² represents an aromatic compound, an alicyclic compound or an imide ring.
In the aromatic compound, the number of elements forming one ring is 5 or more and 8 or less, and a single ring or two rings may be condensed. Specifically, it is a benzene ring, a fused aromatic ring or a heterocyclic ring.
The number of condensed aromatic rings is not particularly limited, but is preferably 2 or more and 5 or less because heat resistance and optical properties tend to be compatible.
The heterocycle is not particularly limited, and specific examples thereof include furan, thiophene, pyrrole, imidazole, pyridine, pyrimidine, pyrazine, oxazole, benzimidazole, benzoxazole and the like.
Examples of the substituent which the aromatic compound may have include an alkyl group having 1 or more and 6 or less carbon atoms, an alkoxy group having 1 or more and 6 or less carbon atoms, an amino group, a hydroxyl group and the like.
The alkyl group having 1 or more and 6 or less carbon atoms and the alkoxy group having 1 or more and 6 or less carbon atoms may have a substituent.
Examples of the substituent which the alkyl group having 1 or more and 6 or less carbon atoms may have include a halogen atom and a hydroxyl group.
The substituent which the alkoxy group having 1 or more and 6 or less carbon atoms may have includes a halogen atom, a hydroxyl group and the like.

The number of carbon atoms forming one ring in the alicyclic compound is 4 or more and 8 or less, and a single ring or two rings may be condensed. In addition, the ring may have an unsaturated bond.
Specifically, cyclobutane, cyclobutadiene, cyclopentane, cyclopentaene, cyclohexane, cyclohexaene, cyclohexadiene, cycloheptane, cycloheptaene, cyclooctane and the like can be mentioned.
The alicyclic compound may have a substituent, and as the substituent which the alicyclic compound may have, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an amino group Groups, hydroxyl groups and the like. The alkyl group having 1 or more and 6 or less carbon atoms and the alkoxy group having 1 or more and 6 or less carbon atoms may have a substituent, and the substituent which may be possessed is the same as the above-mentioned aromatic compound It is synonymous with the thing.

  The imide ring is a ring having an imide bond, and the number of elements forming one ring is 4 or more and 6 or less, and may be only the imide ring or may be condensed with another ring. The ring which may be fused is an aromatic compound which may have a substituent or an alicyclic compound which may have a substituent. The number of rings in the case of condensation is not particularly limited, but is preferably 2 or more and 4 or less because heat resistance and optical characteristics tend to be compatible.

  It is preferable from the point of an optical characteristic improvement that it is a site | part chosen from the structure represented by following formula (31)-(35) among the structures represented by Formula (30).

In formula (31), R ¹⁰ and R ¹¹ each independently represent an alkyl group, an amino group or a hydroxyl group, and Y ¹ and Y ² each independently represent an aromatic hydrocarbon, an alicyclic compound or an imide ring Represents
The alkyl group of R ¹⁰ and R ¹¹ preferably has 1 or more carbon atoms. On the other hand, 10 or less is preferable, 8 or less is still more preferable, and 6 or less is especially preferable. Within this range, the linear expansion coefficient tends to be low, which is preferable. In addition, the alkyl group may have a substituent. Examples of the substituent which the alkyl group may have include a halogen atom, a cyano group, a nitro group, a sulfo group and the like. Among these, unsubstituted or halogen atoms are preferable, and a fluorine atom is particularly preferable. Within this range, the linear expansion coefficient tends to be low.
Y ¹ and Y ² are each as Y ¹ and Y ² of Formula (30) interchangeably, examples, preferred ranges, and the substituent which may have also the same.

Wherein ^{(32), R} 12 ~R ¹⁵ each independently represent an alkyl group or a hydroxyl group.
Alkyl groups R ¹² to R ¹⁵ are each independently, 1 or more carbon atoms are preferred. On the other hand, 10 or less is preferable, 8 or less is still more preferable, and 6 or less is especially preferable. Within this range, the linear expansion coefficient tends to be low, which is preferable. In addition, the alkyl group may have a substituent. Examples of the substituent which the alkyl group may have include a halogen atom, a cyano group, a nitro group, a sulfo group and the like. Among these, a halogen atom is preferable, and a fluorine atom is particularly preferable. Within this range, the linear expansion coefficient tends to be low.
Y ¹ and Y ² are each as Y ¹ and Y ² of Formula (30) interchangeably, examples, preferred ranges, and the substituent which may have also the same.

Wherein (33), ^{Y 1} and ^{Y 2} are each as ^{Y 1} and ^{Y 2} of Formula (30) interchangeably, examples, preferred ranges, and the substituent which may have also the same.

In formula (34), R ¹⁶ represents an alkyl group or an aromatic compound. Y ¹ and Y ² are each as Y ¹ and Y ² of Formula (30) interchangeably, examples, preferred ranges, and the substituent which may have also the same.
The alkyl group of R ¹⁶ preferably has 1 or more carbon atoms. On the other hand, 10 or less is preferable, 8 or less is still more preferable, and 6 or less is especially preferable. Within this range, the linear expansion coefficient tends to be low, which is preferable. In addition, the alkyl group may have a substituent. Examples of the substituent which the alkyl group may have include a halogen atom, a cyano group, a nitro group, a sulfo group and the like. Among these, a halogen atom is preferable, and a fluorine atom is particularly preferable. Within this range, the linear expansion coefficient tends to be low.
The number of elements forming one ring of the aromatic compound of R ¹⁶ is 5 or more and 8 or less, and a single ring or two rings may be condensed. Specifically, it is a benzene ring, a fused aromatic ring or a heterocyclic ring. Among these, a single-ring benzene ring and a fused aromatic ring in which a benzene ring is condensed are preferable because the linear expansion coefficient tends to be low.
The number of condensed aromatic rings is not particularly limited, but is preferably 2 or more and 5 or less because heat resistance and optical properties tend to be compatible.
The heterocycle is not particularly limited, and specific examples thereof include furan, thiophene, pyrrole, imidazole, pyridine, pyrimidine, pyrazine, oxazole, benzimidazole, benzoxazole and the like.
Examples of the substituent which the aromatic compound may have include an alkyl group having 1 or more and 6 or less carbon atoms, an alkoxy group having 1 or more and 6 or less carbon atoms, an amino group, a hydroxyl group and the like.
The alkyl group having 1 or more and 6 or less carbon atoms and the alkoxy group having 1 or more and 6 or less carbon atoms may have a substituent.
Examples of the substituent which the alkyl group having 1 or more and 6 or less carbon atoms may have include a halogen atom and a hydroxyl group.
The substituent which the alkoxy group having 1 or more and 6 or less carbon atoms may have includes a halogen atom, a hydroxyl group and the like.

  In formula (35), R represents an alkyl group, a nitro group, an amino group, a hydroxyl group or a halogen atom.

The alkyl group is not particularly limited, but preferably has 1 or more carbon atoms. On the other hand, 8 or less is preferable and 5 or less is still more preferable. By being in these ranges, the compatibility with the solvent tends to be improved.
The alkyl group may have a substituent, and examples thereof include an amino group, a hydroxyl group, a nitro group, a halogen atom and the like.

  Examples of the diamine residue having a structure represented by the formula (35) include 2,6-diaminotoluene, 2,5-diaminotoluene, 2,4-diaminotoluene, 3,4-diaminotoluene, and 2,3. -Diaminotoluene, 4-fluoro-1,2-phenylenediamine, 4-fluoro-1,3-phenylenediamine, 4-nitro-1,2-phenylenediamine, 4-nitro-1,3-phenylenediamine, 2- Nitro-1,2-phenylenediamine, 3-trifluoromethyl-1,5-phenylenediamine, 4-trifluoromethyl-1,5-phenylenediamine, 4-trifluoromethyl-1,2-phenylenediamine, 3- Hydroxy-1,5-phenylenediamine, 4-hydroxy-1,5-phenylenediamine, 4-hydroxy-1,2-phenyl Derived diamine residue from a diamine compound such Nirenjiamin like.

  Examples of tetracarboxylic acid residues in which two or more aromatic rings are linked via a quaternary carbon atom include 9,9-bis (3,4-dicarboxyphenyl) fluorene dianhydride, 4,4′-isopropylene Phenyldiphthalic anhydride, 2,2-bis (3,4-dicarboxyphenyl) -1,1,1,3,3,3-hexafluoropropane dianhydride, 2,2-bis (2,3 Tetracarboxylic acid residues derived from tetracarboxylic acid dianhydrides such as -dicarboxyphenyl) -1,1,1,3,3,3-hexafluoropropane dianhydride.

  Examples of tetracarboxylic acid residues in which two or more aromatic rings are linked by a hexavalent sulfur atom include, for example, 3,3 ′, 4,4′-diphenyl sulfone tetracarboxylic acid dianhydride, 2,3, 3 ', 4'- diphenyl sulfone tetracarboxylic acid dianhydride, 2, 2', 3, 3 'diphenyl sulfone tetracarboxylic acid dianhydride, 4, 4'-[p- sulfonyl bis (phenylene sulfanyl)] diphthalic acid And tetracarboxylic acid residues derived from tetracarboxylic acid dianhydrides such as anhydrides, 3,3 '-[p-sulfonylbis (phenylenesulfanyl)] diphthalic anhydride and the like.

  Examples of the diamine residue in which two or more aromatic rings are linked by a quaternary carbon atom include, for example, 2,2-bis (4-aminophenyl) hexafluoropropane and 2,2-bis (3-aminophenyl) hexa Fluoropropane, 2,2-bis (4-aminophenyl) propane, 2,2-bis (3-aminophenyl) propane, 1,3-bis [2- (4-aminophenyl) -2-propyl] benzene, 1,4-bis [2- (4-aminopheny) -2-propyl] benzene, 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, 2,2-bis (3-amino-4) -Hydroxyphenyl) propane, 9,9-bis (4-aminophenyl) fluorene, 9,9-bis (3-aminophenyl) fluorene, 9,9-bis (2-aminophen) F) fluorene, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis [4- From diamine compounds such as {4-amino-2- (trifluoromethyl) phenoxy} phenyl] hexafluoropropane and 2,2-bis {4- (4-aminophenoxy) -3,5-dibromophenyl} hexafluoropropane The derived diamine residue is mentioned.

  Examples of the diamine residue in which two or more aromatic rings are connected by a hexavalent sulfur atom include, for example, 4,4′-diaminodiphenyl sulfone, 3,3′-diaminodiphenyl sulfone, 3,4′-diaminodiphenyl sulfone 4,4′-bis (4-aminophenylenesulfanyl) diphenyl sulfone, 3,3′-bis (4-aminophenylenesulfanyl) diphenyl sulfone, bis [4- (4-aminophenoxy) phenyl] sulfone, bis [4 Derived from diamine compounds such as-(3-aminophenoxy) phenyl] sulfone, 2,2-bis (3-amino-4-hydroxyphenyl) sulfone, 3,3 ', 4,4'-tetraaminodiphenyl sulfone The diamine residue is mentioned.

(Physical properties of polyimide precursor and / or polyimide contained in composition)
The weight average molecular weight (Mw) of the polyimide precursor and / or the polyimide contained in the composition is not particularly limited, but is usually 1000 or more, preferably 3000 or more, more preferably 5000 or more, more preferably in weight average molecular weight in terms of polystyrene. It is 10000 or more. Also, it is usually at most 200,000, preferably at most 180000, and more preferably at most 150,000. By being in this range, solubility, solution viscosity, composition viscosity, melt viscosity, and the like are preferable because they fall within a range that can be easily handled by ordinary manufacturing equipment. In addition, the weight average molecular weight of polystyrene conversion can be calculated | required by gel permeation chromatography (GPC).

  The number average molecular weight (Mn) of the polyimide precursor and / or the polyimide contained in the composition is not particularly limited, but the number average molecular weight in terms of polystyrene is usually 500 or more, preferably 1000 or more, more preferably 2500 or more, more preferably It is over 5000. Also, it is usually 100,000 or less, preferably 90000 or less, more preferably 80000 or less. By being in this range, solubility, solution viscosity, composition viscosity, melt viscosity, and the like are preferable because they fall within a range that can be easily handled by ordinary manufacturing equipment. The number average molecular weight of the polyimide precursor and / or the polyimide can be measured by the same method as the weight average molecular weight.

  The molecular weight distribution (PDI, (weight-average molecular weight / number-average molecular weight (Mw / Mn))) of the polyimide precursor and / or the polyimide contained in the composition is usually 1 or more, preferably 1.1 or more, more preferably 1 2 or more, and usually 10 or less, preferably 9 or less, more preferably 8 or less. It is preferable that the molecular weight distribution be in this range in that there is a tendency to obtain a highly homogeneous composition. Moreover, in the prevention of film whitening, by being in the above range, a film having excellent uniformity of components in the film, suppression of whitening, and smoothness of the film tends to be obtained. The molecular weight distribution of the polyimide precursor precursor and / or the polyimide can be determined from the value of the weight average molecular weight and the number average molecular weight.

  The imidation ratio of the polyimide precursor contained in a polyimide precursor composition does not have a restriction | limiting in particular. Usually, it is less than 100%, preferably 80% or less, more preferably 60% or less, further preferably 50% or less, there is no lower limit, and the imidation ratio may be 0%. When the imidation ratio is in this range, the solubility in the solvent used for the polyimide precursor composition becomes high, and the stability of the polyimide precursor composition tends to increase, which is preferable. The imidation ratio of the polyimide precursor contained in a polyimide precursor composition can be calculated | required by the conventionally well-known method, for example, the NMR method, IR method, a titration method, etc.

(Polyimide precursor and / or other components of polyimide composition)
The polyimide precursor and / or polyimide composition of the present invention can contain other components in addition to the above-described polyimide precursor and / or polyimide and solvent as long as the effects of the present invention are not impaired. As other components, for example, surfactants, solvents, antioxidants, lubricants, colorants, stabilizers, UV absorbers, antistatic agents, flame retardants, plasticizers, mold release agents, leveling agents, antifoaming agents Etc. In addition, if necessary, inorganic fillers or organic fillers such as powders, granules, plates and fibers may be blended within a range not to impair the object of the invention. These additive components may be added at any stage of any process of producing the polyimide precursor and / or the polyimide composition.

  Among these components, it is preferable to include a leveling agent because the smoothness of the film tends to be improved. As a leveling agent, a silicone type compound etc. are mentioned, for example. The silicone compound is not particularly limited. For example, polyether modified siloxane, polyether modified polydimethylsiloxane, polyether modified hydroxyl group-containing polydimethylsiloxane, polyether modified polymethylalkyl siloxane, polyester modified polydimethylsiloxane, polyester modified hydroxyl group Containing polydimethylsiloxane, polyester-modified polymethylalkylsiloxane, aralkyl-modified polymethylalkylsiloxane, highly polymerized silicone, amino-modified silicone, amino derivative silicone, phenyl-modified silicone, polyether-modified silicone and the like.

(Production of Polyimide Precursor Contained in Composition)
The reaction for obtaining a polyimide precursor from tetracarboxylic acid dianhydride and a diamine compound can be carried out under conventionally known conditions. There is no limitation in particular in the addition order and the addition method of tetracarboxylic dianhydride and a diamine compound. For example, a polyimide precursor is obtained by charging tetracarboxylic acid dianhydride and a diamine compound in order into a solvent and stirring at an appropriate temperature.

The amount of the diamine compound is usually 0.7 mol or more, preferably 0.8 mol or more, and usually 1.3 mol or less, preferably 1.2 mol or less, relative to 1 mol of tetracarboxylic acid dianhydride. By setting the diamine compound in such a range, the yield of the obtained polyimide precursor tends to be improved.
When the amount of the diamine compound is in this range, the viscosity of the composition tends to be in the range suitable for coating, and a tough film tends to be easily obtained.

  The concentrations of the tetracarboxylic acid dianhydride and the diamine compound in the solvent can be appropriately set according to the reaction conditions and the viscosity of the polyimide precursor. For example, the total mass% of tetracarboxylic acid dianhydride and diamine compound is not particularly limited, but is usually 1 mass% or more, preferably 5 mass% or more, and usually 70 mass% or less, preferably to the total liquid volume. Is 50% by mass or less, more preferably 40% by mass or less. By setting the reaction substrate in this range, a polyimide precursor can be obtained at low cost and with a good yield. Furthermore, molecular weight elongation tends to easily occur, the viscosity does not become too high, and the solution tends to be easy to stir.

The reaction temperature is not particularly limited as long as the reaction proceeds, but is usually 0 ° C. or more, preferably 20 ° C. or more, and is usually 120 ° C. or less, preferably 100 ° C. or less. The reaction time is usually 1 hour or more, preferably 2 hours or more, and usually 100 hours or less, preferably 42 hours or less, and more preferably 24 hours or less. By performing the reaction under such conditions, a polyimide precursor can be obtained at low cost and with a good yield.
The pressure at the time of reaction may be either normal pressure, pressure or reduced pressure.
The atmosphere may be under air or inert atmosphere.

  The solvent used in this reaction is not particularly limited, and examples thereof include hydrocarbon solvents such as hexane, cyclohexane, heptane, benzene, toluene, xylene, mesitylene and anisole; carbon tetrachloride, methylene chloride, chloroform and 1,2-dichloroethane Halogenated hydrocarbon solvents such as chlorobenzene, dichlorobenzene and fluorobenzene; ether solvents such as diethyl ether, tetrahydrofuran, 1,4-dioxane and methoxybenzene; ketone solvents such as acetone, methyl ethyl ketone, cyclohexanone and methyl isobutyl ketone; Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl Glycol solvents such as ether acetate; amide solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone; aprotic polar solvents such as dimethyl sulfoxide; pyridine, picoline, lutidine Heterocyclic solvents such as quinoline and isoquinoline; phenolic solvents such as phenol and cresol; and lactone solvents such as γ-butyrolactone, γ-valerolactone and δ-valerolactone. One of these solvents may be used alone, or two or more thereof may be used in any ratio and combination.

The obtained polyimide precursor may be used as it is, or it may be precipitated as a solid by adding it to a poor solvent and then redissolved in another solvent to obtain a polyimide precursor composition.
The poor solvent at this time is not particularly limited and may be appropriately selected depending on the type of the polyimide precursor, but an ether solvent such as diethyl ether or diisopropyl ether; a ketone solvent such as acetone, methyl ethyl ketone, isobutyl ketone, methyl isobutyl ketone; Alcohol solvents such as methanol, ethanol, isopropyl alcohol and the like can be mentioned. Among them, alcohol solvents such as isopropyl alcohol are preferable in terms of efficient precipitation, low boiling point and easy drying. One of these solvents may be used alone, or two or more thereof may be used in any ratio and combination.

  The solvent for dissolving the polyimide precursor is not particularly limited, and examples thereof include hydrocarbon solvents such as hexane, cyclohexane, heptane, benzene, toluene, xylene, mesitylene, anisole, etc .; N, N-dimethylformamide, N, N-dimethylacetamide Amide solvents such as N-methyl-2-pyrrolidone; aprotic solvents such as dimethylsulfoxide; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether acetate etc Solvent; and the like. Among these, anisole, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, ethylene glycol dimethyl ether and ethylene glycol monomethyl ether are particularly preferable. One of these solvents may be used alone, or two or more thereof may be used in any ratio and combination.

The composition of the present invention may contain other solvents without departing from the subject matter of the present invention. The type is not particularly limited, but an alcohol is preferable because the coating property is improved.
The alcohol is not particularly limited. The vapor pressure at 20 ° C. is not particularly limited, but is preferably 50000 Pa or less, more preferably 20000 Pa or less, still more preferably 10000 Pa or less, more preferably 5000 Pa or less. Moreover, there is no lower limit, and a lower one is preferable, for example, 1 Pa or more. When the vapor pressure is in this range, a film having excellent uniformity of the composition and components in the film, suppression of whitening, and smoothness can be obtained.

The boiling point of the alcohol added to the composition is not particularly limited, but is preferably 60 ° C. or more, more preferably 100 ° C. or more, and still more preferably 120 ° C. or more. Moreover, preferably it is 300 degrees C or less, More preferably, it is 280 degrees C or less, More preferably, it is 250 degrees C or less.
When the boiling point is in this range, the change in concentration of the polyimide precursor composition at the time of film formation such as coating decreases, so that a film excellent in uniformity of components in the film, whitening suppression and film smoothness can be obtained. There is a tendency. Furthermore, the residual solvent in the film after drying or heating tends to be reduced.

  The octanol / water distribution coefficient (log)) of the alcohol added to the composition is not particularly limited, but is preferably 0 or more, more preferably 0.5 or more, and still more preferably 1 or more. There is also no upper limit, and a larger one is preferable. In this range, the influence of moisture on the film is reduced, and whitening tends to be suppressed during film formation.

  Although the ratio with respect to the total solvent of the alcohol added to a composition does not have a restriction | limiting in particular, 50 mass% or less is preferable, 30 mass% or less is more preferable, 20 mass% or less is more preferable. Moreover, 0.1 mass% or more is preferable, 0.5 mass% or more is more preferable, 1.0 mass% or more is more preferable. By being in this range, the solubility of the polyimide precursor and / or the polyimide tends to be high, and the whitening during film formation tends to be suppressed.

The alcohol added to the composition is preferably at least one selected from the group consisting of aromatic alcohols, aliphatic alcohols and glycol monoether alcohols. These solvents may be used alone or in any ratio.
Among them, aliphatic alcohols or glycol monoether alcohols are preferable, and aliphatic alcohols are particularly preferable because the solubility of the polyimide precursor and / or the polyimide becomes high.
Among aliphatic alcohols, the number of carbon atoms is preferably 4 or more, and more preferably 5 or more. Moreover, it is preferable that it is 20 or less, and it is still more preferable that it is 15 or less.
In addition, among aliphatic alcohols, it is preferable to have cyclic and branched, and in the case of branching, it is particularly preferable that the branching position is β and / or γ position.
As described above, having a suitable carbon number and / or substitution position tends to increase the solubility of the polyimide precursor and / or the polyimide.

Although the alcohol added to a composition is not specifically limited, Specifically, the following is mentioned.
(Aromatic alcohol)
Examples of the aromatic alcohol include benzyl alcohol, salicyl alcohol, diphenylmethanol, and vanillyl alcohol.

(Fatty alcohol)
Examples of aliphatic alcohols include methanol having 1 carbon; ethanol having 2 carbons; 1-propanol and 2-propanol having 3 carbons; 1-butanol having 4 carbons, 2-butanol and isobutanol And t-butanol; 1-pentanol having 2 carbon atoms, 2-pentanol, 3-pentanol, 2-methyl-1-butanol, 3-methyl-1-butanol and 2-ethyl-1-propanol; carbon The number 6 is 1-hexanol, 2-hexanol, 3-hexanol, 2-methyl-1-pentanol, 3-methyl-1-pentanol, 3-methyl-2-pentanol, 2-methyl-3-pen Tanol, 2-ethyl-1-butanol, 3-ethyl-2-butanol, 2,3-dimethyl-1-butanol and cyclohexa 1-heptanol, 2-heptanol, 3-heptanol, 4-heptanol, 2-methyl-1-hexanol, 2-methyl-3-hexanol, 2-methyl-4-hexanol, Methyl-1-hexanol, 3-methyl-2-hexanol, 3-methyl-4-hexanol, 2-ethyl-1-pentanol, 2-ethyl-3-pentanol, 2,2-dimethyl-1-pentanol 2,3-Dimethyl-1-pentanol and 2,4-Dimethyl-1-pentanol; 1-octanol, 2-octanol, 3-octanol, 4-octanol, 2-methyl-1-, having 8 carbon atoms Heptanol, 2-methyl-3-heptanol, 2-methyl-4-heptanol, 2-ethyl-1-hexanol, 2-ethyl-3-hexanol Xanol, 2-ethyl-4-hexanol, 2-propyl-1-pentanol, 2-propyl-3-pentanol, 2-propyl-4-pentanol, 2,3-dimethyl-1-hexanol and 2,4 Dimethyl-1-hexanol; 1-nonanol having a carbon number of 9, 2-nonanol, 3-nonanol, 4-nonanol, 5-nonanol, 2-methyl-1-octanol, 2-methyl-3-octanol, 2- Methyl-4-octanol, 2-methyl-5-octanol, 2-methyl-6-octanol, 2-ethyl-1-heptanol, 2-ethyl-3-heptanol, 2-ethyl-4-heptanol, 2-ethyl- 5-heptanol, 2,6-dimethyl-1-heptanol, 2,6-dimethyl-4-heptanol, 3,5,5-trime Thiyl-1-hexanol, 3,5,5-trimethyl-2-hexanol and 2,2,4-trimethyl-1-hexanol; 1-decanol, 2-decanol, 3-decanol, 4-decanol having 10 carbon atoms , 5-decanol, 2-methyl-1-nonanol, 2-methyl-3-nonanol, 2-methyl-4-nonanol, 2-methyl-5-nonanol, 2-ethyl-1-octanol, 2-ethyl-3 Octanol, 2-ethyl-4-octanol and 2-ethyl-5-octanol; 1-undecanol, 2-undecanol, 3-undecanol, 4-undecanol, 4-undecanol, 2-methyl-1-decanol, 2-ethyl having 11 carbon atoms -1-nonanol and 2-propyl-1-octanol; 1-dodecanol having 12 carbon atoms, 2-dodecanol Kanol, 3-dodecanol, 1-ethyl-1-decanol, 2-ethyl-1-decanol, 3-ethyl-1-decanol and 2-butyl-1-octanol; 1-tridecanol having 13 carbon atoms, 2-tridecanol 3-tridecanol, 1-ethyl-1-undecanol, 2-ethyl-1-undecanol, 3-ethyl-1-undecanol and 2-butyl-1-nonanol; 1-tetradecanol which has 14 carbon atoms, 2-tetra Decanol, 3-tetradecanol, 2-methyl-1-tridecanol, 2-ethyl-1-dodecanol and 2-propyl-1-undecanol; 1-pentadecanol, 2-pentadecanol having 15 carbon atoms, 3-pentadecanol, 2-methyl-1-tetradecanol, 2-ethyl-1-tride And 2-propyl-1-dodecanol; 1-hexadecanol which has 16 carbon atoms, 2-hexadecanol, 3-hexadecanol, 2-methyl-1-pentadecanol, 2-ethyl-1-tetra Decanol and 2-propyl-1-tridecanol; 1-heptadecanol having 17 carbon atoms, 2-heptadecanol, 3-heptadecanol, 2-methyl-1-hexadecanol, 2-ethyl-1-hexadecanol Pentadecanol and 2-propyl-1-tetradecanol; 1-octadecanol having 18 carbon atoms, 2-octadecanol, 3-octadecanol, 2-methyl-1-heptadecanol, 2-ethyl -1-hexadecanol and 2-propyl-1-pentadecanol; 1-nonadecanol having a carbon number of 19; 2-nonadecanol; Nadecanol, 2-methyl-1-octadecanol, 2-ethyl-1-heptadecanol and 2-propyl-1-hexadecanol; 1-eicosanol having a carbon number of 20, 2-eicosanol, 3-eicosanol, 2 -Methyl-1-nonadecanol, 2-ethyl-1-octadecanol and 2-propyl-1-heptadecanol; and the like.

(Glycol monoether alcohol)
Examples of glycol monoether alcohols include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether and the like.

When a film is obtained by applying a polyimide precursor or a composition containing a polyimide to a substrate and heating and / or drying, the obtained film tends to be susceptible to the environment in which the film is formed, such as application. is there. In particular, when coating is performed in a high humidity environment, the solubility of the composition may decrease due to moisture absorption before drying, and a polyimide precursor or a polyimide may be precipitated to make the film white (whitening). In addition, there is a problem that even if drying and heating are performed on the film in which whitening has occurred, the original characteristics of the polyimide such as heat resistance and mechanical characteristics can not be obtained. In order to solve these, the solvent is selected from the group consisting of ether solvents, ketone solvents, amide solvents, sulfone solvents, heterocyclic solvents, phenol solvents, lactone solvents and ester solvents 1 It is also possible to use a solvent (hereinafter referred to as solvent A) which is a species or more and having a vapor pressure of 50000 Pa or less at 20 ° C., and an alcohol (hereinafter referred to as solvent B). The reason why the whitening can be suppressed by containing the solvent A and the solvent B is presumed to be that the hydrophobicity of the whole composition is increased and the moisture absorption is suppressed.
The solvent B is preferably at least one selected from the group consisting of an aromatic alcohol, an aliphatic alcohol and a glycol monoether alcohol. These solvents may be used alone or in any ratio.
Among them, aliphatic alcohols or glycol monoether alcohols are preferable, and aliphatic alcohols are particularly preferable, because the solubility of the polyimide precursor becomes high.
Among aliphatic alcohols, the number of carbon atoms is preferably 4 or more, and more preferably 5 or more. Moreover, it is preferable that it is 20 or less, and it is still more preferable that it is 15 or less.
Further, among aliphatic alcohols, it is preferable to have cyclic and branched, and in the case of branching, it is particularly preferable that the branching position is β and / or γ position.
By having an appropriate carbon number and / or substitution position as described above, the solubility of the polyimide precursor tends to be high.

The vapor pressure difference between the solvent A and the solvent B is not particularly limited, but is preferably 10000 Pa or less, more preferably 5000 Pa or less, still more preferably 1000 Pa or less. Also, there is no lower limit, and the vapor pressure difference may be zero. Furthermore, the vapor pressure of solvent A and solvent B may be either higher.
When the vapor pressure difference is in a specific range, the concentration change of the polyimide precursor composition at the time of film formation such as coating decreases, and therefore, the whitening suppression, the uniformity of the components in the film, and the smoothness of the film are excellent. There is a tendency for films to be obtained. Furthermore, the residual solvent in the film after drying and heating of the film tends to be reduced.

The boiling point difference between the solvent A and the solvent B is not particularly limited, but is preferably 100 ° C. or less, more preferably 80 ° C. or less, still more preferably 50 ° C. or less. Also, there is no lower limit, and the boiling point difference may be zero. Furthermore, either of the boiling points of the solvent A and the solvent B may be higher.
When the boiling point difference is in a specific range, the concentration change of the polyimide precursor composition during film formation is reduced, and therefore, a film excellent in whitening suppression, uniformity of components in the film, and film smoothness can be obtained. There is a tendency. Furthermore, the residual solvent in the film after drying and heating of the film tends to be reduced.

  Although the ratio of the ratio of the solvent A and the solvent B to the total solvent is not particularly limited, 50% by mass or less of the solvent B is preferable, 30% by mass or less is more preferable, and 20% by mass or less preferable. Moreover, 0.1 mass% or more is preferable, 0.5 mass% or more is more preferable, 1.0 mass% or more is more preferable. When the ratio of the ratio of the solvent A to the solvent B is in this range, the solubility of the polyimide precursor is maintained, and the whitening inhibitory effect tends to be obtained.

  A film formed using the above-mentioned solvent is particularly excellent in transparency and low colorability, and thus can be suitably used for applications such as a coating material, a surface protective layer, an adhesive, a substrate for a device, and an insulating film.

(Viscosity of composition)
The viscosity of the composition of the present invention is not particularly limited, but is usually 200 cP or more, preferably 300 cP or more, more preferably 500 cP or more, and usually 200 000 cP or less, preferably 100 000 cP or less, at a viscosity of 20% at 25 ° C. Preferably it is 80000 cP or less. When the viscosity of the composition is in this range, handling at the time of production becomes easy, and the film thickness tends to be uniform at the time of film formation.
The viscosity of the composition can be measured by a conventionally known method. For example, a vibration viscometer, an E-type viscometer, etc. can be used.

(Concentration of composition)
The concentration of the polyimide precursor and / or the polyimide contained in the composition of the present invention is not particularly limited, but usually 3% by mass or more, preferably 5% by mass or more, more preferably 7% by mass or more, and usually 60 It is not more than mass%, preferably not more than 50 mass%, more preferably not more than 45 mass%. When the concentration is in this range, the production is facilitated, and the film thickness tends to be uniform during film formation.
The concentration of the composition can be measured by a conventionally known method. For example, it can be determined by the method described above.

(Production of polyimide contained in composition)
The method for producing the polyimide contained in the composition is not particularly limited. For example, a method of producing a polyimide precursor to obtain a polyimide, a method of directly producing a polyimide from tetracarboxylic acid dianhydride and a diamine compound, or the like can be used.

(Method of manufacturing from polyimide precursor)
A polyimide can be obtained by dehydrating and cyclizing the polyimide precursor obtained by the above method or the like in the presence of a solvent. The imidization can be carried out using any method known in the art, and examples thereof include thermal imidization to thermally cyclize, chemical imidization to chemically cyclize, and the like. These imidization reactions may be performed alone or in combination.

(Heating imidization)
The solvent for imidizing the polyimide precursor may be the same as the solvent used in the reaction for obtaining the polyimide precursor. The solvent for producing the polyimide precursor and the solvent for producing the polyimide may be the same or different.
In this case, water generated by imidization may be discharged out of the system in order to inhibit the ring closure reaction. The concentration of the polyimide precursor during the imidization reaction is not particularly limited, but is usually 1% by mass or more, preferably 5% by mass or more, and usually 70% by mass or less, preferably 40% by mass or less. By carrying out in this range, the production efficiency tends to be high, and the solution viscosity tends to be easy to produce.

The imidization reaction temperature is not particularly limited, but is usually 50 ° C. or more, preferably 80 ° C. or more, more preferably 100 ° C. or more, and usually 300 ° C. or less, preferably 280 ° C. or less, more preferably 250 ° C. or less. By carrying out in this range, the imidization reaction proceeds efficiently, and reactions other than the imidization reaction tend to be suppressed, which is preferable.
The pressure during the reaction may be any of normal pressure, increased pressure and reduced pressure. The atmosphere may be under air or inert atmosphere.

  Moreover, a compound having a function of enhancing nucleophilicity and electrophilicity can also be added as an imidization promoter which promotes imidization. Specifically, for example, trimethylamine, triethylamine, tripropylamine, tributylamine, triethanolamine, N, N-dimethylethanolamine, N, N-diethylethanolamine, triethylenediamine, N-methylpyrrolidine, N-ethylpyrrolidine , Tertiary amine compounds such as N-methylpiperidine, N-ethylpiperidine, imidazole, pyridine, quinoline and isoquinoline; carboxylic acids such as 4-hydroxyphenylacetic acid, 3-hydroxybenzoic acid, N-acetylglycine and N-benzoylglycine Compounds; Polyphenol compounds such as 3,5-dihydroxyacetophenone, methyl 3,5-dihydroxybenzoate, pyrogallol, methyl gallate, ethyl gallate, naphthalene-1,6-diol; 2-hydroxy Lysine, 3-hydroxypyridine, 4-hydroxypyridine, 4-pyridinemethanol, N, N-dimethylaminopyridine, nicotinaldehyde, isonicotinaldehyde, picoline aldehyde, picoline aldehyde oxime, nicotinaldehyde oxime, isonicotinaldehyde oxime, picoline acid Ethyl, ethyl nicotinate, ethyl isonicotinate, nicotinamide, isonicotinamide, 2-hydroxynicotinic acid, 2,2'-dipyridyl, 4,4'-dipyridyl, 3-methylpyridazine, quinoline, isoquinoline, phenanthroline, 1 , 10-phenanthroline, imidazole, benzimidazole, heterocyclic compounds such as 1,2,4-triazole, and the like.

  Among these, tertiary amine compounds or heterocyclic compounds are preferable, and triethylamine, imidazole or pyridine is more preferable because it tends to easily control the imidation ratio. One of these compounds may be used alone, or two or more thereof may be used in any ratio and combination.

The amount of the imidization accelerator used is usually 0.01 mol% or more, preferably 0.1 mol% or more, and more preferably 1 mol% or more, based on the carboxyl group or ester group. Moreover, it is preferable that it is 50 mol% or less, and it is more preferable that it is 10 mol% or less. When the amount of the catalyst used is in such a range, the imidization reaction tends to proceed efficiently, and a polyimide having a controlled imidization ratio can be obtained.
Further, the timing of adding the imidization promoter can be appropriately adjusted in order to obtain a desired imidation ratio, and may be before the start of heating or may be during heating. Moreover, you may divide and add to multiple times.

(Chemical imidization)
A polyimide can be obtained by chemically imidizing a polyimide precursor using a dehydrating condensing agent in the presence of a solvent.
As a solvent used at the time of chemical imidation, the thing similar to the solvent used at the time of reaction which obtains said polyimide precursor is mentioned.

  Examples of the dehydration condensation agent include N, N-disubstituted carbodiimides such as N, N-dicyclohexylcarbodiimide, N, N-diphenylcarbodiimide, etc .; acid anhydrides such as acetic anhydride and trifluoroacetic anhydride; thionyl chloride, tosyl chloride and the like Chloride, acetyl chloride, acetyl bromide, propionyl iodide, acetyl fluoride, propionyl chloride, propionyl bromide, propionyl iodide, propionyl fluoride, isobutyryl chloride, isobutyryl bromide, isobutyryl iodide, isobutyryl Ryl fluoride, n-butyryl chloride, n-butyryl bromide, n-butyryl iodide, n-butyryl fluoride, mono-, di-, tri-chloroacetyl chloride, mono-, di-, tri Bromoacetyl chloride, mono-, di-, tri-iod acetyl chloride, mono-, di-, tri-fluoro acetyl chloride, chloroacetic anhydride, phenyl phosphonic dichloride, thionyl chloride, thionyl bromide, thionyl iodide, thionyl fluoride Halogenated compounds such as lide; phosphorus compounds such as phosphorus trichloride, triphenyl phosphite, diethyl phosphate cyanide; and the like.

  Of these, acid anhydrides and halogenated compounds are preferred, and in particular, acid anhydrides tend to be capable of efficiently advancing the imidization reaction and being able to obtain a polyimide having a controlled imidization rate. preferable. One of these compounds may be used alone, or two or more thereof may be used in any ratio and combination.

  The amount of the dehydrating condensation agent used is usually 0.1 mol or more, preferably 0.2 mol or more, and usually 1.0 mol or less, preferably 0.9 mol or less, per 1 mol of the polyimide precursor. The imidation ratio can be controlled by making a dehydration condensation agent into this range.

  The concentration of the polyimide precursor at the time of the imidization reaction is not particularly limited, but is usually 1% by mass or more, preferably 5% by mass or more, and usually 70% by mass or less, preferably 40% by mass or less. Within this range, the imidization ratio can be controlled, the production efficiency is high, and the solution viscosity tends to be easy to produce.

The imidization reaction temperature is not particularly limited, but is usually 0 ° C. or more, preferably 10 ° C. or more, more preferably 20 ° C. or more, and is usually 150 ° C. or less, preferably 130 ° C. or less, more preferably 100 ° C. or less. It is preferable to carry out the reaction in this range because the imidization reaction proceeds efficiently and a polyimide having a controlled imidization ratio can be obtained. Furthermore, it is preferable because side reactions other than the imidization reaction are suppressed.
The pressure at the time of reaction may be any of normal pressure, pressure and reduced pressure. The atmosphere may be under air or inert atmosphere.

  Also, as a catalyst for promoting imidization, the above-mentioned tertiary amines and the like can be added in the same manner as in the heat imidization.

(Method for producing polyimide from tetracarboxylic acid dianhydride and diamine compound)
A polyimide can be directly obtained from tetracarboxylic acid dianhydride and a diamine compound using a conventionally known method. In this method, synthesis of the imide precursor to imidization is carried out to the imidization without stopping the reaction or isolating the precursor.

  There are no particular limitations on the order of addition and method of addition of the tetracarboxylic acid dianhydride and the diamine compound, but for example, the temperature at which the reaction to imidation proceeds with the tetracarboxylic acid dianhydride and the diamine compound sequentially added to the solvent The polyimide is obtained by stirring with

  The amount of the diamine compound is usually 0.7 mol or more, preferably 0.8 mol or more, and usually 1.3 mol or less, preferably 1.2 mol or less, relative to 1 mol of tetracarboxylic acid dianhydride. By setting the amount of the diamine compound in such a range, a polyimide having a controlled imidization ratio can be obtained, and the yield of the obtained polyimide composition tends to be improved.

  The concentrations of the tetracarboxylic acid dianhydride and the diamine compound in the solvent can be set as appropriate for each condition and the viscosity during polymerization, but the total mass of the tetracarboxylic acid dianhydride and the diamine compound is specifically set. Although not present, it is usually 1% by mass or more, preferably 5% by mass or more, and usually 70% by mass or less, preferably 40% by mass or less, based on the total liquid amount. When the concentration in the solvent is in a suitable range, molecular weight extension tends to occur and stirring tends to be easy.

As the solvent used in this reaction, the same solvents as those used in the reaction for obtaining the above-mentioned polyimide precursor can be mentioned.
Also in the case of obtaining a polyimide from tetracarboxylic acid dianhydride and a diamine compound, heating imidization and / or chemical imidization can be used as in the case of obtaining a polyimide from a polyimide precursor. The reaction conditions and the like of the heat imidization and the chemical imidation in this case are the same as described above.

(Re-precipitation / re-dissolution of polyimide contained in the composition)
The obtained polyimide may be used as it is as a polyimide composition, or it may be used as a polyimide composition by re-dissolving in another solvent after depositing the polyimide into a solid by adding it to a poor solvent. it can.

  The poor solvent at this time is not particularly limited and may be appropriately selected depending on the type of polyimide, but, for example, ether solvents such as diethyl ether and diisopropyl ether; ketone solvents such as acetone, methyl ethyl ketone, isobutyl ketone and methyl isobutyl ketone; Alcohol solvents such as methanol, ethanol and isopropyl alcohol; and the like. Among them, alcohol solvents such as isopropyl alcohol are preferable because the precipitates can be efficiently obtained, the boiling point is low, and the drying tends to be easy. One of these solvents may be used alone, or two or more thereof may be used in any ratio and combination.

  Further, as a solvent for re-dissolving the polyimide, for example, hydrocarbon solvents such as hexane, cyclohexane, heptane, benzene, toluene, xylene, mesitylene, anisole and the like; N, N-dimethylformamide, N, N-dimethylacetamide, N Amide solvents such as methyl-2-pyrrolidone; aprotic solvents such as dimethyl sulfoxide; glycol solvents such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether acetate; Etc. Among these, anisole, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, ethylene glycol dimethyl ether and ethylene glycol monomethyl ether are particularly preferable. One of these solvents may be used alone, or two or more thereof may be used in any ratio and combination.

  The composition of the present invention may contain other solvents without departing from the spirit of the present invention. The type is not particularly limited, but an alcohol is preferable because the coating property is improved. Preferred alcohols are as described above.

  To the composition of the present invention, a coupling agent such as a silane coupling agent or a titanium coupling agent can be added in order to adjust the adhesion to the coated body.

  As a silane coupling agent, for example, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltripropoxysilane, γ-aminopropyltributoxysilane, γ-aminoethyltriethoxysilane, γ -Aminoethyltrimethoxysilane, γ-aminoethyltripropoxysilane, γ-aminoethyltributoxysilane, γ-aminobutyltriethoxysilane, γ-aminobutyltrimethoxysilane, γ-aminobutyltripropoxysilane, γ-amino Butyl tributoxysilane etc. are mentioned.

  As a titanium coupling agent, for example, γ-aminopropyltriethoxytitanium, γ-aminopropyltrimethoxytitanium, γ-aminopropyltripropoxytitanium, γ-aminopropyltributoxytitanium, γ-aminoethyltriethoxytitanium, γ -Aminoethyltrimethoxytitanium, γ-aminoethyltripropoxytitanium, γ-aminoethyltributoxytitanium, γ-aminobutyltriethoxytitanium, γ-aminobutyltrimethoxytitanium, γ-aminobutyltripropoxytitanium, γ-amino Butyl tributoxy titanium and the like can be mentioned.

  One of these coupling agents may be used alone, or two or more thereof may be used in any ratio and combination. The amount used at this time is preferably 0.1% by mass or more and 3% by mass or less with respect to the polyimide.

  In addition, it is also possible to mix various additives as needed. For example, other inorganic fillers such as powdery, granular, plate-like, and fibrous and organic fillers can be blended as long as the effects of the present invention are not impaired.

  These fillers may be processed into a flat plate such as a non-woven fabric or the like, or plural fillers may be mixed and used. Further, if desired, various additives generally used in resin compositions, such as lubricants, colorants, stabilizers, antioxidants, ultraviolet absorbers, antistatic agents, flame retardants, plasticizers, release agents, etc. It can be blended. These various fillers and additives may be added at any stage of any process for producing the polyimide.

(Polyimide)
The polyimide according to the present invention contains a tetracarboxylic acid residue and a diamine residue, and has a partial structure selected as one or more from group III as a tetracarboxylic acid residue and a partial structure selected as one or more from group IV. And a diamine residue having a partial structure represented by the formula (11).

Group III: The following formulas (7) and (8) are shown.

[In formula (7),
X ¹ represents a direct bond, an alkylene group, a carbonyl group, an ether bond or a sulfonyl group. ]

Group IV: The following formulas (9) and (10) are shown.

[In equation (9),
n 'and m' each independently represent 0 or 1;
R ⁵ and R ⁶ each independently represent an alkyl group, an alkenyl group or an aromatic ring. R ⁵ and R ⁶ may be different or the same and may form a ring. ]

[In equation (10),
Y ′ represents a direct bond or a divalent organic group. ]

[In equation (11),
R ⁷ and R ⁸ each independently represent an alkyl group, an alkoxy group, an amino group or a hydroxyl group. ]

X ¹ of Formula (7) is synonymous with X of Formula (1), and the preferable range and the substituent which it may have are also synonymous.
N 'and m' of Formula (9) are respectively synonymous with n and m of Formula (3), and the preferable range is also synonymous. Further, R ⁵ and R ⁶ are each as R ¹ and R ² of formula (3) synonymous with a preferred range and the substituent which may have also the same.
Y 'of Formula (10) is synonymous with Y of Formula (4), and the preferable range and the substituent which it may have are also synonymous.
R ⁷ and R ^{8 in} the formula (11) have the same meanings as R ³ and R ^{4 in} the formula (5), respectively, and the preferable range and the substituent which the group may have are also the same.

The polyimide of the present invention is a tetracarboxylic acid residue having other than the partial structure represented by the above formulas (7), (8), (9) and (10) without departing from the scope of the present invention. You may have. Moreover, you may have the diamine residue which has except the partial structure shown by Formula (11).
Examples of the tetracarboxylic acid residue having a moiety other than the partial structure represented by the above formulas (7), (8), (9) and (10) include the above formulas (1), (2) and (3) And tetracarboxylic acid dianhydrides such as aromatic tetracarboxylic acid dianhydrides and aliphatic tetracarboxylic acid dianhydrides shown as tetracarboxylic acid residues having other than partial structures represented by formula (4) and formula (4) And tetracarboxylic acid residues derived from
As a diamine residue which has other than the partial structure shown by said Formula (11), the diamine residue derived | led-out from the diamine compound shown as a diamine residue which has other than the partial structure represented by said Formula (5) is It can be mentioned.

The polyimide of the present invention preferably has a tetracarboxylic acid residue and / or a diamine residue having a bending site, since this tends to improve the optical properties.
As a tetracarboxylic acid and / or diamine residue having a bending site, a tetracarboxylic acid and / or diamine residue having a bending site which may be possessed by the polyimide precursor and / or the polyimide in the composition of the present invention It is synonymous with group, and its preferable range is also synonymous.

  Among the diamine residues having other than the partial structure represented by Formula (11), it is preferable to have the diamine residue having the partial structure represented by Formula (12) in order to improve the optical properties.

[In equation (12),
Z 'represents a direct bond, a sulfonyl group, an alkylene group, a carbonyl group or an ether bond,
A ′ and B ′ each independently represent a direct bond, a divalent aromatic ring, a divalent heterocyclic ring or a phenyl ether group. ]

  Z ', A' and B 'of Formula (12) are respectively synonymous with Z, A and B of Formula (6), and the preferable range and the substituent which it may have are also synonymous respectively.

The partial structure contained in the polyimide can be determined by analyzing the composition of the raw material monomer by solid NMR, IR or the like.
Moreover, after melt | dissolving with an alkali, it can obtain | require by gas chromatography (GC), < ¹ > H-NMR, < ¹³ > C-NMR, two-dimensional NMR, mass spectrometry etc.

  Although the shape of the polyimide of this invention is not specifically limited, For example, various forms, such as a powder form, pellet form, a film form, can be taken.

  The polyimide of the present invention is preferably soluble in a solvent. Soluble in a solvent is as defined above, and the solvent used is also synonymous. By being soluble in a solvent, processing such as casting and coating becomes possible, and at that time, processing can be performed under mild conditions because it does not involve an imidization reaction. In addition, the storage stability of the solution can be improved.

(The nature of polyimide)
The properties and properties of the polyimide of the present invention are not particularly limited without departing from the spirit of the present invention.

The tensile strength of the polyimide of the present invention is not particularly limited, but is usually 50 MPa or more, preferably 70 MPa or more, and usually 400 MPa or less, preferably 300 MPa or less.
The tensile modulus of elasticity is not particularly limited, but is usually 1000 MPa or more, preferably 1500 MPa or more, and usually 20 GPa or less, preferably 10 GPa or less.
The tensile elongation is not particularly limited, but is usually 5% GL or more, preferably 10% GL or more, more preferably 20 GL% or more, and usually 300% GL or less, preferably 200 GL% or less.
By being in the range as described above, it has strength and is particularly useful in forming a film. The tensile strength, the tensile elastic modulus and the tensile elongation can be determined, for example, by measuring a film-like polyimide with a tensile tester.

  The glass transition temperature of the polyimide of the present invention is not particularly limited, but is usually 100 ° C. or more, preferably 150 ° C. or more, more preferably 200 ° C. or more. Heat resistance can be acquired because glass transition temperature is this range. The glass transition temperature can be measured, for example, by using differential scanning calorimetry, viscoelasticity measurement, thermogravimetric / differential thermal simultaneous analysis or the like.

  The linear expansion coefficient of the polyimide of the present invention is usually 60 ppm / K or less, preferably 50 ppm / K or less, more preferably 45 ppm / K or less, still more preferably 40 ppm / K, particularly preferably 100 ppm to 150 DEG C. It is 30 ppm / K or less. Within this range, for example, when manufacturing a device using polyimide as a film, dimensional stability is high, and breakage and deformation of members such as electronic elements and color filters are less likely to occur, which is preferable. Although a measuring method is not specifically limited, For example, it can measure by the method of an Example using a film-form polyimide.

  The transmittance of the polyimide of the present invention is a film, and when the film thickness is 1 to 100 μm, the transmittance to a light of 500 nm is usually 55% or more, preferably 60% or more, more preferably 70% or more. The emission efficiency of the device can be effectively used by being in this range. The transmittance can be measured by the method described in JIS K 7361-1 (1997).

  The retardation when using the polyimide of the present invention as a film is a wavelength used, for example, an arbitrary wavelength between 400 and 800 nm for device applications, and the retardation (Rth) in the thickness direction of the film is usually 300 nm or less Preferably it is 200 nm or less, more preferably 170 nm or less, still more preferably 150 nm or less, still more preferably 140 nm or less, particularly preferably 120 nm or less. The retardation (R0) in the in-plane direction of the film is usually 10 nm or less, preferably 5 nm or less, more preferably 3 nm or less, and still more preferably 1 nm or less. This range is preferable because the visibility of the device is improved.

  The polyimides of the present invention are useful for film applications. In addition to film applications, application to a wide range of applications is possible. For example, it can be used for manufacturing a member for a flexible solar cell, a member for a display, a liquid crystal display carrier, a heat resistant insulating tape, a heat resistant adhesive tape or a film for a capacitor or a flexible printed substrate. For example, it is used also for manufacture of a structural member reinforced with glass fiber, carbon fiber, etc., a molded product of a bobbin of a small coil, or a tube for terminal insulation.

  Moreover, it can use for manufacture of laminated materials, such as an insulation spacer, a magnetic head spacer, or a spacer of a transformer. It can also be used in the manufacture of enamel coatings such as wire and cable insulation, low temperature storage tanks, space insulation or integrated circuits. Furthermore, it can be used for the production of yarn, woven fabric or non-woven fabric having heat resistance.

(Polyimide film)
In addition to the polyimide film using the polyimide according to the present invention, a polyimide film having the following features is also preferably used.
That is, the present invention is a polyimide film containing a tetracarboxylic acid residue and a diamine residue, wherein at least one of the tetracarboxylic acid residue and the diamine residue has a bending site, and the linear expansion coefficient is 60 ppm / The present invention also relates to a polyimide film characterized by having a K or less and a retardation of 200 nm or less.
The definition of the inflection point of at least one of the tetracarboxylic acid residue and the diamine residue is the same as the inflection point described above, and the preferred structure is also the same.

  The linear expansion coefficient of the polyimide film may be 60 ppm / K or less, preferably 50 ppm / K or less, more preferably 45 ppm / K or less, still more preferably 40 ppm / K, particularly preferably 30 ppm / K or less. Moreover, there is no lower limit and the lower one is preferable. Within this range, for example, when manufacturing a device using polyimide as a film, dimensional stability is high, and breakage and deformation of members such as electronic elements and color filters are less likely to occur, which is preferable. Although a measuring method is not specifically limited, For example, it can measure by the method of an Example using a film-form polyimide.

The method for setting the linear expansion coefficient of the polyimide film to 60 ppm / K or less is not particularly limited. For example, a method using a composition containing at least one of the above-mentioned polyimide precursor and polyimide, a method of adding a filler, etc. The linear expansion coefficient of a polyimide film can be made into the said range by performing the method of extending | stretching etc. and adjusting these suitably.
The filler and the like are not particularly limited, and examples thereof include inorganic fillers such as powdery, granular, plate-like and fibrous and organic fillers.

  As the inorganic filler, for example, oxides such as silica, kieselguhr, barium ferrite, beryllium oxide, pumice, pumice balloon and the like; hydroxides such as aluminum hydroxide, magnesium hydroxide, basic magnesium carbonate and the like; calcium carbonate , Carbonates such as magnesium carbonate, dolomite and dawsonite; sulfates and sulfites such as calcium sulfate, barium sulfate, ammonium sulfate and calcium sulfite; talc, clay, mica, asbestos, glass fibers, glass balloons, glass beads, calcium silicate Silicate such as montmorillonite and bentonite; Carbons such as carbon fiber, carbon black, graphite and carbon hollow spheres; powder such as molybdenum sulfide, zinc borate, barium metaborate, calcium borate, sodium borate and boron fiber , Granular, plate , Fibrous inorganic fillers; powdered, granular, fibrous, whisker-like metallic fillers such as metal elements, metal compounds and alloys; silicon carbide, silicon nitride, zirconia, aluminum nitride, titanium carbide, potassium titanate, etc. Powdery, granular, fibrous, whisker-like ceramic fillers; and the like.

On the other hand, examples of organic fillers include carbon nanotubes, fullerenes, aromatic polyamide fibers, cellulose fibers, nylon fibers, polyester fibers, polypropylene fibers, thermosetting resin powder, rubber and the like.
As a filler, what was processed into flat form, such as a nonwoven fabric, may be used, and a plurality of materials may be mixed and used.
The linear expansion coefficient can be measured by a thermomechanical device.

The retardation of the polyimide film may be 200 nm or less, preferably 170 nm or less, more preferably 150 nm or less, still more preferably 140 nm or less, particularly preferably 120 nm or less. The retardation (R0) in the in-plane direction of the film is usually 10 nm or less, preferably 5 nm or less, more preferably 3 nm or less, and still more preferably 1 nm or less. This range is preferable because the visibility of the device is improved.
The method for setting the retardation of the polyimide film to 200 nm or less is not particularly limited. For example, a method using a composition containing at least one of the above-mentioned polyimide precursor and polyimide, a method of mixing a compound having negative retardation or a resin The retardation of a polyimide film can be made into the said range by using the method of forming into a film using the base material which has a linear expansion coefficient equivalent to a polyimide.
Although the compound or resin which has a negative retardation is not specifically limited, For example, a styrene compound, an acryl compound, a styrene resin, an acrylic resin etc. are mentioned.
A metal foil, a resin substrate, etc. are mentioned as a base material which has a linear expansion coefficient equivalent to a polyimide.
The retardation can be measured by a retardation film / optical material inspection device or the like.

  The transmittance of the polyimide film of the present invention is usually 55% or more, preferably 60% or more, more preferably 70% or more, for a light of 500 nm when the film thickness is 1 to 100 μm. The emission efficiency of the device can be effectively used by being in this range. The transmittance can be measured by the method described in JIS K 7361-1 (1997).

  In the polyimide film of the present invention, the yellowness (yellow index: YI) at a film thickness of 10 μm is usually −10 or more, preferably −5 or more, more preferably −1 or more. On the other hand, it is usually 20 or less, preferably 15 or less, more preferably 10 or less. By setting it as this range, when using a polyimide as a device member, the efficiency of light emission can be used effectively. The yellow index can be measured, for example, by using a spectral colorimeter or the like.

  The thickness of the polyimide film is not particularly limited, but is usually 1 μm or more, preferably 2 μm or more, and is usually 200 μm or less, preferably 100 μm or less. The appropriate thickness of the film maintains sufficient resistance and enables thinning of the flexible device.

(Method for producing polyimide film)
Although the method for producing the polyimide film of the present invention is not particularly limited, for example, it is obtained by evaporating the solvent after applying the polyimide precursor obtained by the method and / or the composition containing the polyimide on a carrier substrate. be able to. The method of application is not particularly limited as long as it can form a layer having a uniform thickness, but, for example, die coating, spin coating, screen printing, spraying, casting using an applicator, method using a coater, spraying Methods, immersion methods, calendar methods, casting methods and the like can be mentioned. These methods can be appropriately selected according to the application area, the shape of the application surface, and the like.

  As a board | substrate of to-be-coated material, the board | substrate consisting of plastics, such as glass, such as float glass and soda glass, a polyethylene terephthalate, a polycarbonate, polyolefin, can be used, for example. When applying to such a substrate, the functional silane-containing compound and the functional titanium-containing compound may be put on the surface of the substrate in advance. In addition, ultraviolet treatment, plasma treatment, and the like can also be performed.

  The method for volatilizing the solvent of the polyimide precursor and / or the polyimide composition is also not particularly limited. Usually, the solvent is volatilized by a method of volatilizing the solvent under reduced pressure and / or by heating the coated material to be coated. The heating method is not particularly limited, and examples thereof include hot air heating, vacuum heating, infrared heating, microwave heating, heating by contact using a hot plate or a hot roll, and the like.

The heating temperature for volatilizing the solvent may be any suitable temperature depending on the type of solvent, but usually 20 ° C. or higher, preferably 40 ° C. or higher, more preferably 50 ° C. or higher, further preferably 60 ° C. or higher It is. The temperature is usually 400 ° C. or less, preferably 380 ° C. or less, more preferably 350 ° C. or less, and still more preferably 300 ° C. or less. When the temperature is at least the above lower limit, the residual solvent can be reduced and sufficient drying can be performed. Moreover, by being below the said upper limit, the air bubble etc. which generate | occur | produce by sudden volatilization can be suppressed, and an external appearance and quality can be kept favorable.
The heating atmosphere may be under air or an inert atmosphere, and is not particularly limited. However, when colorless transparency is required for the polyimide film, heating may be performed under an inert atmosphere such as nitrogen to suppress coloring. preferable.

  Although the method to peel off the polyimide film formed on the carrier by the said application | coating and drying does not have a restriction | limiting in particular, For example, laser peeling, mechanical peeling, the peeling by immersion in water or hot water, etc. are mentioned.

  As a method of producing a film and / or a polyimide film using a polyimide precursor composition, a method of melting and molding the polyimide precursor resin and / or the polyimide resin, for example, an injection molding method, an extrusion molding method, a hollow molding Methods, compression molding methods, lamination methods, roll processing methods, stretching methods, stamp processing methods, heat press methods, T-die methods and the like.

  Hereinafter, the present invention will be described in more detail by way of examples and comparative examples. The following examples are presented to explain the present invention in detail, and the present invention is not limited to the following examples as long as the gist of the present invention is not violated. The values of various conditions and evaluation results in the following examples also have meaning as preferable values of the upper limit or lower limit in the embodiment of the present invention, and the preferable range is the value of the upper limit or lower limit described above It may be a range defined by the values of the embodiment or a combination of the values of the embodiments.

Example 1
3,5 g (0.019 mol) of 3,3 ′, 4,4′-biphenyltetracarboxylic acid dianhydride (BPDA) in a four-necked flask equipped with a reflux nitrogen gas inlet tube, a condenser, and a stirrer 2.6 g (0.009 mol) of 3 ', 4,4'-bicyclohexanetetracarboxylic acid dianhydride (H-BPDA), 1.4 g (0.006 mol) of pyromellitic anhydride (PMDA), 2,2 5.6 g (0.018 mol) of '-bis (trifluoromethyl) benzidine (6F-m-TB), 4.3 g (0.018 mol) of 4,4'-diaminodiphenyl sulfone, N-methyl-2-pyrrolidone 73 g of NMP was added. The mixture was heated with stirring and reacted at 80 ° C. for 6 hours to obtain Composition 1 containing a polyimide precursor.

(Preparation of polyimide film)
The obtained composition 1 was applied onto a glass substrate using a 100 μm applicator, and heated at 350 ° C. for 30 minutes to obtain a polyimide film 1 with a film thickness of 10 μm.

(Measurement of coefficient of linear expansion (CTE))
A polyimide film 1 that has been conditioned in a constant temperature and humidity chamber with a temperature of 25 ° C and humidity of 50% overnight is punched out using a super straight cutter with a width of 4 mm and a length of 40 mm, and measured using TMA / SS6100 manufactured by SII Nano Technology. did. The distance between chucks of the film sample is 10 mm, nitrogen 120 mL / min, CTE between 100 ° C. and 150 ° C. at a heating rate of 10 ° C./min from 30 ° C. to 210 ° C. is described in Table 2.

(Measurement of retardation (Rth) value in the film thickness direction)
The retardation (Rth) value in the thickness direction of the film of the polyimide film 1 was measured and calculated using a retardation film / optical material inspection apparatus (“RETS 100” manufactured by Otsuka Electronics Co., Ltd.). The measurement results are shown in Table 2. The retardation (Rth) value in the thickness direction of the film used this time is a value at a wavelength of 460 nm and a film thickness of 10 μm.

(Measurement of yellow index (YI) value)
The yellow index (YI) value of the polyimide film 1 was measured using SM color computer SM5 manufactured by Suga Test Instruments Co., Ltd. The YI value used this time is a value calculated as a YI value per film thickness of 10 μm.

Example 2
1.7 g (0.006 mol) of BPAD of Example 1, 1.8 g (0.006 mol) of H-BPDA, 3.9 g (0.018 mol) of PMDA, 5.5 g of 6F-m-TB 017 mol), polyimide precursor composition 2 and polyimide film 2 in the same manner as in Example 1 except that 3.2 g (0.013 mol) of 4,4'-diaminodiphenyl sulfone and 65 g of NMP were used. Obtained. The CTE, Rth and YI of the polyimide film were measured in the same manner as in Example 1. The results are shown in Table 2.

[Example 3]
Example 1 5.3 g (0.018 mol) of BPDA, 2.5 g (0.008 mol) of H-BPDA, 1.3 g (0.006 mol) of PMDA, 7.9 g of 6F-m-TB Polyimide precursor composition 3 and polyimide film 3 in the same manner as in Example 1 except that 0.25 g of 4,4'-diaminodiphenyl sulfone was changed to 2.0 g (0.008 mol) and NMP was changed to 71 g. Obtained. The CTE, Rth and YI of the polyimide film were measured in the same manner as in Example 1. The results are shown in Table 2.

Example 4
5.4 g (0.018 mol) of BPDA of Example 1, 2.5 g (0.008 mol) of H-BPDA, 1.3 g (0.006 mol) of PMDA, 9.5 g of 6F-m-TB .3 mol), a polyimide precursor composition 4 and a polyimide film 4 were obtained in the same manner as in Example 1 except that 0.8 g (0.003 mol) of 4,4'-diaminodiphenyl sulfone and 78 g of NMP were used. The The CTE, Rth and YI of the polyimide film were measured in the same manner as in Example 1. The results are shown in Table 2.

[Example 5]
In a four-necked flask equipped with a reflux nitrogen gas inlet tube, a condenser, a Dean-Stark agglomerator filled with toluene, and a stirrer, 4.9 g (0.017 mol) BPDA, 2.3 g (0.007 mol) H-BPDA, PMDA1 .2 g (0.006 mol), 6F-m-TB 8.6 g (0.027 mol), 4,4'-diaminodiphenyl sulfone 0.7 g (0.003 mol), NMP 71 g and toluene 14 g were added. The mixture was heated under reflux at 200 ° C. for 13 hours while being stirred to obtain a polyimide composition 5.

[Example 6]
4.1 g (0.014 mol) of BPDA of Example 1, 2.1 g (0.007 mol) of H-BPDA, 1.9 g (0.009 mol) of PMDA, 8.4 g (0 g of 6F-m-TB) .026 mol), 2.2 g (0.009 mol) of 4,4'-diaminodiphenyl sulfone, 82 g of NMP, and 1.9 g of 3,3 ', 4,4'-diphenyl sulfone tetracarboxylic acid dianhydride The polyimide precursor composition 6 and the polyimide film 6 were obtained in the same manner as in Example 1 except that (0.005 mol) was added. The CTE, Rth and YI of the polyimide film were measured in the same manner as in Example 1. The results are shown in Table 2.

[Example 7]
5.4 g (0.018 mol) of BPDA of Example 6, 1.2 g (0.004 mol) of H-BPDA, 1.3 g (0.006 mol) of PMDA, 3,3 ', 4,4'-diphenyl 1.5 g (0.004 mol) of sulfonetetracarboxylic acid dianhydride, 7.9 g (0.025 mol) of 6F-m-TB, 2.0 g (0.008 mol) of 4,4'-diaminodiphenyl sulfone, A polyimide precursor composition 7 and a polyimide film 7 were obtained in the same manner as in Example 6 except that the NMP was changed to 78 g. The CTE, Rth and YI of the polyimide film were measured in the same manner as in Example 1. The results are shown in Table 2.

[Example 8]
5.4 g (0.018 mol) of BPDA of Example 6, 2.0 g (0.007 mol) of H-BPDA, 1.3 g (0.006 mol) of PMDA, 3,3 ', 4,4'-diphenyl 0.6 g (0.002 mol) of sulfonetetracarboxylic acid dianhydride, 7.9 g (0.025 mol) of 6F-m-TB, 2.0 g (0.008 mol) of 4,4'-diaminodiphenyl sulfone, A polyimide precursor composition 8 and a polyimide film 8 were obtained in the same manner as in Example 6 except that the NMP was changed to 77 g. The CTE, Rth and YI of the polyimide film were measured in the same manner as in Example 1. The results are shown in Table 2.

[Example 9]
Example 6 5.9 g (0.019 mol) of BPDA, 1.9 g (0.006 mol) of H-BPDA, 1.4 g (0.006 mol) of PMDA, 7.7 g (0 g of 6F-m-TB) .024 mol), 1.2 g (0.005 mol) of 4,4'-diaminodiphenyl sulfone, 76 g of NMP, and 9,3 ', 4,4'-diphenyl sulfone tetracarboxylic acid dianhydride The polyimide precursor composition 9 and the polyimide film 9 were obtained in the same manner as in Example 6 except that the 9-bis (4-aminophenyl) fluorene was changed to 1.1 g (0.003 mol). The CTE, Rth and YI of the polyimide film were measured in the same manner as in Example 1. The results are shown in Table 2.

[Example 10]
9.8 g (0.033 mol) of BPDA of Example 6, 2.3 g (0.007 mol) of H-BPDA, 2.4 g (0.011 mol) of PMDA, 18.0 g (0 g of 6F-m-TB) .56 mol), 4.7 g (0.019 mol) of 4,4'-diaminodiphenyl sulfone, and 141 g of NMP, and 2,3,3 ', 4,4'-diphenyl sulfone tetracarboxylic acid dianhydride Example 6 is similar to Example 6 except that 2-bis (3,4-dicarboxyphenyl) -1,1,1,3,3,3-hexafluoropropane dianhydride is changed to 9.9 g (0.022 mol) The polyimide precursor composition 10 and the polyimide film 10 were obtained by the method. The CTE, Rth and YI of the polyimide film were measured in the same manner as in Example 1. The results are shown in Table 2.

[Example 11]
3.8 g (0.013 mol) of BPDA of Example 10, 2.0 g (0.007 mol) of H-BPDA, 1.7 g (0.008 mol) of PMDA, 2,2-bis (3,4-di) 2.1 g (0.005 mol) of carboxyphenyl) -1,1,1,3,3,3-hexafluoropropane dianhydride, 7.9 g (0.025 mol) of 6F-m-TB, 4,4 The polyimide precursor composition 11 and the polyimide film 11 were obtained in the same manner as in Example 10 except that 2.0 g (0.008 mol) of '-diaminodiphenyl sulfone and 79 g of NMP were used. The CTE, Rth and YI of the polyimide film were measured in the same manner as in Example 1. The results are shown in Table 2.

[Example 12]
Example 10 except that 6.6 g (0.022 mol) of BPDA of Example 10, 2.2 g (0.007 mol) of H-BPDA, 4.9 g (0.022 mol) of PMDA, and 139 g of NMP were used. The polyimide precursor composition 12 and the polyimide film 12 were obtained in the same manner as in the above. The CTE, Rth and YI of the polyimide film were measured in the same manner as in Example 1. The results are shown in Table 2.

[Example 13]
5.2 g (0.018 mol) of BPDA of Example 9, 1.8 g (0.006 mol) of H-BPDA, 1.3 g (0.006 mol) of PMDA, 6.2 g of 6F-m-TB 020 mol), 1.9 g (0.008 mol) of 4,4'-diaminodiphenyl sulfone, 53 g of NMP, and 9,9-bis (4-aminophenyl) fluorene as 2,2-bis (3-) The polyimide precursor composition 13 and the polyimide film 13 were obtained in the same manner as in Example 9 except that amino-4-hydroxyphenyl) -hexafluoropropane was changed to 1.1 g (0.003 mol). The CTE, Rth and YI of the polyimide film were measured in the same manner as in Example 1. The results are shown in Table 2.

Example 14
6.6 g (0.022 mol) of BPAD of Example 1, 3.0 g (0.010 mol) of H-BPDA, 1.6 g (0.007 mol) of PMDA, 9.6 g (0 g of 6F-m-TB) .030 mol), NMP was changed to 73 g, and 4,4'-diaminodiphenyl sulfone was changed to 3.4 g (0.010 mol) of 1,4-bis [2- (4-aminophenyl) -2-propyl] benzene The polyimide precursor composition 14 and the polyimide film 14 were obtained in the same manner as in Example 1 except for the above. The CTE, Rth and YI of the polyimide film were measured in the same manner as in Example 1. The results are shown in Table 2.

[Example 15]
The 1,4-bis [2- (4-aminophenyl) -2-propyl] benzene of Example 14 is changed to 1,3-bis [2- (4-aminophenyl) -2-propyl] benzene Example 13 A polyimide precursor composition 14 and a polyimide film 14 were obtained in the same manner as described above. The CTE, Rth and YI of the polyimide film were measured in the same manner as in Example 1. The results are shown in Table 2.

Comparative Example 1
In a four-necked flask equipped with a refluxing nitrogen gas inlet tube, a condenser, and a stirrer, 4.4 g (0.015 mol) BPDA, 2.3 g (0.008 mol) H-BPDA, 3.3 g (0.015 mol) PMDA, 6F- 12.2 g (0.038 mol) of m-TB and 76 g of NMP were added. The mixture was heated with stirring and reacted at 80 ° C. for 6 hours to obtain a composition 16 containing a polyimide precursor. A polyimide film 16 was obtained from the obtained composition 16 in the same manner as in Example 1. The CTE, Rth and YI of the polyimide film were measured in the same manner as in Example 1. The results are shown in Table 2.

Comparative Example 2
In a four-necked flask equipped with a reflux nitrogen gas inlet tube, a condenser and a stirrer, 1.8 g (0.006 mol) of H-BPDA, 5.2 g (0.024 mol) of PMDA, 7.2 g (0.023 mol) of 6F-m-TB ), 1.9 g (0.008 mol) of 4,4'-diaminodiphenyl sulfone and 64 g of NMP were added. The mixture was heated with stirring and reacted at 80 ° C. for 6 hours to obtain Composition 17 containing a polyimide precursor. A polyimide film 17 was obtained from the obtained composition 17 in the same manner as in Example 1. The CTE, Rth and YI of the polyimide film were measured in the same manner as in Example 1. The results are shown in Table 2.

Comparative Example 3
In a four-necked flask equipped with a refluxing nitrogen gas inlet tube, a condenser, a Dean-Stark coagulator filled with anisole, and a stirrer, 14.6 g (0.050 mol) BPDA, 15.2 g (0.050 mol) H-BPDA, 6F- 16.0 g (0.05 mol) of m-TB, 9.9 g (0.04 mol) of 4,4'-diaminodiphenyl sulfone, 2.5 g (0.01 mol) of 3,3'-diaminodiphenyl sulfone, 87 g of NMP, 87 g of anisole added. The mixture was heated to reflux at 200 ° C. for 13 hours while being stirred, to obtain a polyimide composition 18. A polyimide film 18 was obtained from the obtained composition 18 in the same manner as in Example 1. The CTE, Rth and YI of the polyimide film were measured in the same manner as in Example 1. The results are shown in Table 2.

Comparative Example 4
5.6 g (0.019 mol) of BPAD of Example 1, 1.4 g (0.006 mol) of PMDA, 7.7 g (0.024 mol) of 6F-m-TB, 4,4'-diaminodiphenyl sulfone 2.0 g (0.008 mol), NMP was changed to 76 g and H-BPDA was changed to 2.3 g (0.006 mol) of 3,3 ', 4,4'-diphenyl sulfone tetracarboxylic acid dianhydride The polyimide precursor composition 19 and the polyimide film 19 were obtained in the same manner as in Example 1. The CTE, Rth and YI of the polyimide film were measured in the same manner as in Example 1. The results are shown in Table 2.

Comparative Example 5
In a four-necked flask equipped with a refluxing nitrogen gas inlet tube, a condenser, and a stirrer, 3.6 g (0.012 mol) of BPDA, 3.8 g (0.012 mol) of H-BPDA, 2,2'-dimethylbenzidine (m-TB) ) (38 g) of N, N-dimethylacetamide (DMAc) was added. The mixture was heated with stirring and reacted at 80 ° C. for 6 hours to obtain a composition 21 containing a polyimide precursor. A polyimide film 21 was obtained from the obtained composition 21 in the same manner as in Example 1. The CTE, Rth and YI of the polyimide film were measured in the same manner as in Example 1. The results are shown in Table 2.

Comparative Example 6
In a four-necked flask equipped with a refluxing nitrogen gas inlet tube, a condenser, and a stirrer, 5.8 g (0.02 mol) of BPDA, 6.4 g (0.020 mol) of 6F-m-TB, N, N-dimethylacetamide (DMAc) Added 37 g. The mixture was heated with stirring and reacted at 80 ° C. for 6 hours to obtain a composition 22 containing a polyimide precursor. A polyimide film 22 was obtained from the obtained composition 22 in the same manner as in Example 1. The CTE, Rth and YI of the polyimide film were measured in the same manner as in Example 1. The results are shown in Table 2.

Comparative Example 7
In a four-necked flask equipped with a reflux nitrogen gas inlet tube, a condenser, and a stirrer, 21.2 g (0.069 mol) of H-BPDA, 14.7 g (0.070 mol) of m-TB, and 108 g of DMAc were added. The mixture was heated with stirring and reacted at 80 ° C. for 6 hours to obtain a composition 23 containing a polyimide precursor. A polyimide film 23 was obtained from the obtained composition 23 in the same manner as in Example 1. The CTE, Rth and YI of the polyimide film were measured in the same manner as in Example 1. The results are shown in Table 2.

Comparative Example 8
Comparative Example 7 and Comparative Example 7 except that H-BPDA of Comparative Example 7 was changed to 6.8 g (0.022 mol), m-TB to 5.9 g (0.023 mol) of 4,4'-diaminodiphenyl sulfone, and DMAc to NMP 37 g The polyimide precursor composition 24 and the polyimide film 24 were obtained by the same method. The CTE, Rth and YI of the polyimide film were measured in the same manner as in Example 1. The results are shown in Table 2.

Comparative Example 9
3.2 g (0.015 mol) of PMDA of Comparative Example 2, 8.8 g (0.027 mol) of 6F-m-TB, 69 g of NMP, and 4.4 g (0.015 mol) of BPDA in BPDA, Polyimide precursor composition 25 and polyimide in the same manner as in Comparative Example 2 except that 4,4'-diaminodiphenylsulfone was changed to 9,9-bis (4-aminophenyl) fluorene 0.9 g (0.003 mol) The film 25 was obtained. The CTE, Rth and YI of the polyimide film were measured in the same manner as in Example 1. The results are shown in Table 2.

[Reference Example 1]
BPDA of Comparative Example 6 was treated with 8.7 g (0.020 mol) of 2,2-bis (3,4-dicarboxyphenyl) -1,1,1,3,3,3-hexafluoropropane dianhydride, 6F- A polyimide precursor composition 26 and a polyimide film 26 were obtained in the same manner as in Comparative Example 6 except that m-TB was changed to 6.4 g (0.02 mol) and DMAc to 46 g. The CTE, Rth and YI of the polyimide film were measured in the same manner as in Example 1. The results are shown in Table 2.

[Reference Example 2]
2.9 g (0.01 mol) BPDA, 3.0 g (0.01 mol) H-BPDA, 6.4 g (0.020 mol) 6 F-m-TB in a four-necked flask equipped with a reflux nitrogen gas inlet tube, a condenser, and a stirrer. ), 37 g of N, N-dimethylacetamide (DMAc) were added. The mixture was heated with stirring and reacted at 80 ° C. for 6 hours to obtain a composition 20 containing a polyimide precursor. A polyimide film 20 was obtained from the obtained composition 20 in the same manner as in Example 1. The CTE, Rth and YI of the polyimide film were measured in the same manner as in Example 1. The results are shown in Table 2. Further, in the above raw materials, the ratio of the tetracarboxylic acid dianhydride to the diamine compound was adjusted so that the viscosity of the composition was 200 to 600 cP, to obtain a composition 27. The ratio is shown in Table 3.
Composition 27 was applied onto a glass substrate and heated as in Example 1. When peeling the obtained film, a crack occurred and a film could not be obtained.
On the other hand, the ratio of the tetracarboxylic dianhydride to the diamine compound of the raw material used in Example 7 was adjusted so that the viscosity of the composition was 200 to 600 cP, to obtain a composition 28. The ratio is shown in Table 3.
Composition 28 was applied onto a glass substrate and heated as in Example 1. The resulting film was able to be peeled off without cracking or the like.

  As shown in Table 2, it was shown that the polyimide films 1 to 15 of the present invention have both low linear expansion coefficient and low retardation. On the other hand, it was shown that the polyimide film shown in the comparative example can not simultaneously achieve low linear expansion coefficient and low retardation.

  As shown in Reference Example 2 and Table 3, in the composition 28 containing the bending site, film formation was possible even if the viscosity was reduced to 200 to 600 cP, but the composition not containing the bending site In No. 27, it was difficult to form a film when the viscosity was reduced, and it is shown that the composition can be obtained in a wide viscosity range by having a bending portion, and it becomes possible to apply to various coating methods. The

  Although the invention has been described in detail and with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention. The present application is a Japanese patent application filed on Feb. 21, 2014 (Japanese Patent Application No. 2014-032147), a Japanese patent application filed on June 26, 2014 (Japanese Patent Application No. 2014-131668), and a Japanese patent application filed on January 6, 2015 This is based on Japanese Patent Application (Japanese Patent Application No. 2015-000993), the contents of which are incorporated herein by reference.

  The polyimide precursor composition of the present invention can be used as a coating material, a surface protective layer, an adhesive, a device substrate, an insulating film, and the like.

Claims (2)

A polyimide film comprising a tetracarboxylic acid residue and a diamine residue, wherein
The tetracarboxylic acid residue has a partial structure selected from one or more from group I shown below and a partial structure selected from one or more from group II shown below,
The diamine residue has a partial structure represented by the following formula (5),
At least one of the tetracarboxylic acid residue and the diamine residue has a bending site represented by the following formula (30) :
Linear expansion coefficient is 60 ppm / K or less, and
A polyimide film having a retardation of 200 nm or less.
Group I: partial structure represented by the following formula (1) and partial structure represented by the following formula (2):
[In formula (1),
X represents a direct bond, an alkylene group, a carbonyl group, an ether bond or a sulfonyl group. ]
Group II: partial structure represented by the following formula (3) and partial structure represented by the following formula (4):
[In equation (3),
n and m each independently represent 0 or 1;
R ¹ and R ² each independently represent an alkylene group, an alkenylene group or an aromatic ring.
R ¹ and R ² may be bonded to each other to form a ring. ]
[In Formula (4), Y shows a direct bond or a bivalent organic group. ]
[In formula (5),
R ³ and R ⁴ each independently represent an alkyl group, an alkoxy group, an amino group or a hydroxyl group. ]
[In equation (30),
Z ¹ represents a quaternary carbon atom, a hexavalent sulfur atom, a tertiary amine or a benzene ring.
Y ¹ and Y ² each independently represent a cyclic structure. ]   The polyimide film of Claim 1 whose yellow index in case the film thickness of a film is 10 micrometers is -10 or more and 20 or less.