TWI568716B - Resin precursor and resin composition containing the same, resin film and method for producing the same, and layered product and method for producing the same - Google Patents

Description

Resin precursor, resin composition containing the same, resin film, method for producing the same, laminated body and method for producing the same

The present invention relates to a resin precursor used in a substrate for a flexible device, a resin composition containing the same, a resin film, a method for producing the same, a laminate, and a method for producing the same.

In general, in applications requiring high heat resistance, a film of a polyimide pigment (PI) resin is used as the resin film. In general, a polyimine resin is obtained by solution polymerization of an aromatic dianhydride and an aromatic diamine to produce a polyimide precursor, which is then subjected to ring closure dehydration at a high temperature to carry out thermal hydrazine imidization or use of a catalyst. A high heat resistant resin produced by chemical hydrazine imidization.

The polyimide resin is an insoluble and non-fusible super heat resistant resin, and has excellent properties such as heat oxidation resistance, heat resistance, radiation resistance, low temperature resistance, and chemical resistance. Therefore, the polyimide resin is used for electronic materials including an insulating coating agent, an insulating film, a semiconductor, and an electrode protective film of a TFT-LCD (Thin Film Transistor-Liquid Crystal Display). In a wide range of fields, the industry is currently researching a glass substrate that is used in the field of display materials such as liquid crystal alignment films, and uses a colorless transparent flexible substrate that utilizes its lightness and flexibility.

However, the usual polyimide resin is colored brown or yellow due to the higher aromatic ring density, and the transmittance in the visible light region is low, and it is difficult to use in the field requiring transparency.

In order to improve the transparency of such a polyimide, for example, it is described in Non-Patent Document 1. The polyimine which enhances the transmittance and the transparency of the hue by using an acid dianhydride containing a specific structure and a diamine containing a specific structure is contained. Further, Patent Documents 1 to 4 disclose the use of 4,4-bis(diaminodiphenyl)fluorene (hereinafter, also referred to as 4,4-DAS) or 3,3-bis(diaminodiyl). Phenyl)anthracene (hereinafter also referred to as 3,3-DAS) and a polyimine which contains a specific structure of acid dianhydride to improve the transparency and the transparency of the hue.

Further, in Examples 9 and 10 of the following Patent Document 6, it is described that by copolymerizing a specific aromatic tetracarboxylic dianhydride with an alicyclic diamine or a hydrazine-containing diamine, a high Tg can be produced. Polyimine precursor of polyimine which is transparent, high-density and low warpage.

Further, in the third embodiment of Patent Document 7 and the third embodiment of Patent Document 8, the use of aromatic tetracarboxylic dianhydride, bis(diaminodiphenyl)fluorene, and hydrazine-containing diamine is described. The polymerized polyimide precursor is used as a semiconductor protective resin and a photosensitive resin composition.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 61-141732

[Patent Document 2] Japanese Patent Laid-Open No. Hei 06-271670

[Patent Document 3] Japanese Patent Laid-Open No. 09-040774

[Patent Document 4] Japanese Patent Laid-Open Publication No. 2000-313804

[Patent Document 5] International Publication No. 2012/118020

[Patent Document 6] International Publication No. 2011/122198

[Patent Document 7] International Publication No. 1991/010699

[Patent Document 8] Japanese Patent Laid-Open No. Hei 4-224823

[Non-patent literature]

[Non-Patent Document 1] Latest Polyimine (Basic and Applied), edited by Japan Polyimine Research Society, P152

However, the physical properties of the known transparent polyimide are used as, for example, a semiconductor insulating film, a TFT-LCD insulating film, an electrode protective film, an ITO (Indium Tin Oxides) electrode substrate for touch panel, and flexibility. The display is not sufficient for a heat-resistant colorless transparent substrate.

For example, when a polyimide resin is used for a colorless transparent substrate for a flexible display, a polyimide film is formed on a supporting glass (hereinafter, also referred to as a support), and is usually formed on a polyimide film thereof. A TFT element is produced, and an inorganic film is sometimes formed for this purpose. In the case where the linear expansion coefficient (hereinafter also referred to as CTE) of polyimine is high, the polyimide film and the inorganic film are used due to the mismatch of the inorganic film or the CTE of the support glass and the polyimide film. Residual stress is generated between them, and as a result, there is a problem that the support glass is warped or the performance of the TFT element is lowered. Therefore, there is a problem of reducing the residual stress of the polyimine in order to improve the warpage of the supporting glass. In the polyimine disclosed in Patent Documents 1 to 4, when residual stress is high and it is applied to a colorless transparent substrate for a flexible display, there is a problem that warpage of the supporting glass occurs.

Further, in order to produce a polyimide film, it is generally required to apply, for example, a polyimide precursor on a glass substrate, and to apply a glass substrate coated with the polyimide precursor to a baking furnace into which nitrogen gas is introduced. Heating is carried out at 250 ° C to 400 ° C (hereinafter also referred to as a curing step). In the polyimine which improves the transmittance and the transparency of the hue described in Patent Documents 1 to 4 or Non-Patent Document 1, when the oxygen concentration in the baking furnace at the time of curing is high, specifically, the oxygen concentration is In the case of 100 ppm or more, there is a problem that the YI (Yellowness Index) value is increased or the oxygen concentration dependence of the total light transmittance is lowered.

Further, when a polyimide resin is used for a colorless transparent substrate for a flexible display, a TFT element is usually formed on the upper portion of the polyimide film by a photolithography step using a photoresist. Polyimine film for use in a colorless transparent substrate for flexible displays (hereinafter, also referred to as a polyimide substrate), in order to expose it to a chemical such as a photoresist stripper used in the step of removing the photoresist contained in the step, it is necessary to treat the chemical It has chemical resistance. The polyimine containing 4,4-DAS or 3,3-DAS and an acid dianhydride having a specific structure as described in Patent Document 1 has the following problems in chemical resistance: in the photoresist stripping step When a small amount of cracks are generated on the polyimide substrate, the polyimide substrate is white turbid, and the total light transmittance is lowered.

Patent Document 5 describes that a soft bismuth-containing diamine is introduced by block copolymerization in order to reduce residual stress while maintaining the glass transition temperature or the Young's modulus of the polyimide. However, as described in Comparative Example 4 of Patent Document 5, when block copolymerization of a ruthenium-containing diamine is carried out, a polyoxonium precursor is not dissolved in a combination of a special solvent, and a polyoxonium portion is carried out. Separation, in a sea-island structure in which the refractive indices are different, the structure of the island portion is increased, causing the film to become cloudy and the total light transmittance is lowered. Further, in the case of using a combination of special solvents having a relatively low boiling point, if the polyimide precursor solution is applied to a substrate and left at room temperature for several hours, haze is generated and the coating film is cloudy. Situation, so the placement time needs to be managed. As described above, in order to produce a transparent thermosetting film by performing block copolymerization of a hydrazine-containing diamine to form a transparent thermosetting film, there is a problem in that it is necessary to dissolve a precursor by using a combination of special solvents, and to apply the coating. The placement time after the precursor solution is managed.

Further, in Examples 9 and 10 of Patent Document 6, a polyimine precursor obtained by copolymerizing an aromatic tetracarboxylic dianhydride, an alicyclic diamine, and a polydecane diamine is described and Polyimine obtained from a quinone imine precursor. However, as confirmed by the inventors of the present invention, the polyamine has a problem that the yellowness is high, the total light transmittance is low, and the yellowness and the transmittance are easily affected by the oxygen concentration at the time of hardening of the polyimide. Effect (refer to Comparative Example 25 of the specification of the present application).

Further, Patent Documents 7 and 8 disclose a polyimine precursor obtained by copolymerizing (diaminodiphenyl)fluorene, an aromatic tetracarboxylic dianhydride, and a polydecanediamine, and the polymerization.醯 Polyimine obtained from an imine precursor. However, as confirmed by the inventors of the present invention, there have been problems in that the quality of the monomer having a mercapto group relative to the mercapto group-containing monomer or polycarboxylic acid derivative used in synthesizing the polyimine precursor is as follows. The ratio of the total mass of the diamine compound is small in Patent Document 7, and thus the residual stress of the obtained polyimine is large, which is not suitable for the process of the display, and on the other hand, it is larger in Patent Document 8. Thus, the obtained polyimine produced white turbidity and was not suitable for use in a transparent display (refer to Comparative Examples 23 and 24 of the specification of the present application).

The present invention has been developed in view of the above-described problems, and an object thereof is to provide a resin precursor which can obtain a transparent resin cured product without a combination of special solvents and which can be provided between the inorganic film and the inorganic film. The resulting cured resin has a low residual stress and excellent chemical resistance, and has a small influence on the YI value and the total light transmittance caused by the oxygen concentration in the curing step. Moreover, an object of the present invention is to provide a resin composition containing the resin precursor, a resin film obtained by curing the resin composition, a method for producing the same, a laminate, and a method for producing the same.

The inventors of the present invention have made in an effort to solve the above problems, and have found that a heat-resistant resin precursor having a specific structure can form a transparent resin cured product without a combination of special solvents, and the resin cured product is A resin cured product having a low residual stress generated between the inorganic films and excellent chemical resistance and having a small influence on the YI value or the total light transmittance caused by the oxygen concentration at the curing step is completed based on the knowledge. The invention has been made. That is, the present invention is as follows.

[1] A resin precursor obtained by polymerizing a polymerization component containing an amine group and an amine group reactive group, and the polymerization component comprises two or more selected from the group consisting of an amine group and an amine group reactive group. a polyvalent compound comprising a mercapto group-containing compound comprising a diamine represented by the following formula (1):

The resin precursor has a structure represented by the following formula (2):

In the formula, a plurality of R ₃ and R ₄ are each independently a one-carbon organic group having 1 to 20 carbon atoms, and h is an integer of 3 to 200, and the amount of the compound containing a mercapto group is The total mass basis is 6 mass% to 25% by mass.

[2] The resin precursor according to [1], wherein the amine-based reactive group contains at least one selected from the group consisting of a carboxyl group, a substituted carboxyl group, and an acid anhydride group.

[3] The resin precursor according to [1] or [2], wherein the thiol group-containing compound comprises a polyfluorene oxide compound represented by the following formula (3):

In the formula, a plurality of R ₂ are independently a single bond or a divalent organic group having 1 to 20 carbon atoms, and R ₃ and R ₄ are each independently a one-carbon organic group having 1 to 20 carbon atoms, and a plurality of organic groups may exist. R _{5 is} independently a monovalent organic group having 1 to 20 carbon atoms, and L ₁ , L ₂ and L ₃ are each independently an amine group, an isocyanate group, a carboxyl group, an acid anhydride group, an acid ester group, a fluorenyl group, a hydroxyl group, and a ring. An oxy or fluorenyl group, j is an integer from 3 to 200, and k is an integer from 0 to 197}.

[4] The resin precursor according to [3], wherein, in the formula (3), L ₁ and L ₂ are each independently an amine group or an acid anhydride group, and k is 0.

[5] The resin precursor according to [4], wherein, in the formula (3), both of L ₁ and L ₂ are an amine group.

[6] The resin precursor according to any one of [1] to [5] wherein the resin precursor contains the unit 1 and the unit 2, and the unit 1 has at least the structure represented by the following formula (4):

In the formula, there are a plurality of R ₁ independently being a hydrogen atom, a carbon number of 1 to 20, a monovalent aliphatic hydrocarbon group or a monovalent aromatic group, and there may be a plurality of X ₁ independently of carbon numbers 4 to 32. a tetravalent organic group, and n is an integer of from 1 to 100}, and the unit 2 has a structure represented by the following formula (5):

In the formula, a plurality of R ₁ are independently a hydrogen atom, a carbon number of 1 to 20, a monovalent aliphatic hydrocarbon group or a monovalent aromatic group, and a plurality of R ₂ are independently 3 to 20 carbon atoms. a valence aliphatic hydrocarbon group or a divalent aromatic group, R ₃ and R ₄ are each independently a one-carbon organic group having 1 to 20 carbon atoms, and a plurality of X ₂ organic groups independently having a carbon number of 4 to 32 may be present. , l is an integer from 3 to 50, and m is an integer from 1 to 100} or a structure represented by the following general formula (6):

In the formula, there are a plurality of R ₁ independently being a hydrogen atom, a carbon number of 1 to 20, a monovalent aliphatic hydrocarbon group or a monovalent aromatic group, and a plurality of R ₃ and R ₄ are independently a carbon number 1~ 20 one-valent organic group, a plurality of R ₈ are independently a trivalent aliphatic hydrocarbon group or a trivalent aromatic group having 3 to 20 carbon atoms, p is an integer of 1 to 100, and q is an integer of 3 to 50 } or both the structure represented by the above formula (5) and the structure represented by the above formula (6).

[7] The resin precursor according to [6], wherein the total amount of the unit 1 and the unit 2 is 30% by mass or more based on the total mass of the resin precursor.

[8] The resin precursor of [6] or [7], wherein the resin precursor further contains a unit 3 having a structure represented by the following formula (7): [Chem. 7]

In the formula, a plurality of R ₁ are independently a hydrogen atom, a carbon number of 1 to 20, a monovalent aliphatic hydrocarbon group or a monovalent aromatic group, and a plurality of X ₃ may be independently a carbon number of 4 to 32. The divalent organic group may have a plurality of X ₄ independently independently a tetravalent organic group having a carbon number of 4 to 32, and t is an integer of 1 to 100.

[9] The resin precursor according to [8], wherein, in the formula (7), X ₃ is a structure obtained by removing an amine group from 2,2'-bis(trifluoromethyl)benzidine, that is, a residue.

[10] The resin precursor according to any one of [6] to [9] wherein the unit 1 and the unit 2 comprise the total amount of the unit derived from the acid dianhydride of the unit 1 and the unit 2 a portion which is a combination of the following two parts in an amount of 60 mol% or more, which is derived from a mixture selected from the group consisting of pyromellitic dianhydride (PMDA) and biphenyltetracarboxylic dianhydride (BPDA). One or more sites in the group, and the origin is selected from 4,4'-oxydiphthalic dianhydride (ODPA), 4,4'-(hexafluoroisopropylidene) diphthalic anhydride (6FDA), cyclohexane-1,2,4,5-tetracarboxylic dianhydride (CHDA), 3,3',4,4'-diphenylphosphonium tetracarboxylic dianhydride (DSDA), 4, One or more of 4'-biphenyl bis(trimellitic acid monoester anhydride) (TAHQ) and 9,9'-bis(3,4-dicarboxyphenyl)ruthenium hydride (BPAF) The part.

[11] The resin precursor according to any one of [1] to [10] wherein the R ₃ and the R ₄ are each independently a monovalent aliphatic hydrocarbon group having 1 to 3 carbon atoms or a carbon number of 6 to 10 A monovalent aromatic hydrocarbon group.

[12] The resin precursor according to any one of [1] to [11] wherein the R ₃ and at least a part of the R ₄ are a phenyl group.

[13] The resin precursor according to any one of [1] to [12] wherein the resin precursor is obtained by heat-hardening the resin precursor under an inert gas atmosphere at 300 to 500 ° C. At least one glass transition temperature in the region of -150 ° C ~ 0 ° C and at least one glass transition temperature in the region of 150 ° C ~ 380 ° C, and in the region greater than 0 ° C less than 150 ° C does not have glass transition temperature .

[14] The resin precursor according to any one of [1] to [13] which comprises a source of 20 mol% or more based on the total amount of the acid dianhydride-derived portion of the resin precursor. The site of benzenetetracarboxylic dianhydride (BPDA).

[15] The resin precursor according to any one of [1] to [14], wherein a part thereof is imidized by hydrazine.

[16] A precursor mixture comprising the resin precursor according to any one of [1] to [15] and a resin precursor having a structure represented by the following formula (8):

In the formula, a plurality of X ₃ may be independently a tetravalent organic group having a carbon number of 4 to 32, and a plurality of R ₁ are independently a hydrogen atom, a carbon number of 1 to 20, a monovalent aliphatic hydrocarbon group or a Avalent aromatic group, and r is an integer from 1 to 100}.

[17] A flexible device material comprising the resin precursor according to any one of [1] to [15] or the precursor mixture such as [16].

[18] A resin film which is a cured product of a resin precursor according to any one of [1] to [15] or a cured product of a precursor mixture such as [16].

[19] A resin composition containing the resin precursor according to any one of [1] to [15] or a precursor mixture such as [16] and a solvent.

[20] The resin composition according to [19], wherein the resin composition is on the surface of the support After being expanded, the resin composition is heated at 300 ° C to 500 ° C in a nitrogen atmosphere to obtain a resin obtained by subjecting the resin precursor contained in the resin composition to imidization. When the film thickness is 20 μm, the yellowness is 7 or less.

[21] The resin composition according to [19] or [20], wherein after the resin composition is developed on the surface of the support, the resin composition is subjected to a nitrogen atmosphere at 300 ° C to 500 ° C. The resin obtained by subjecting the resin precursor contained in the resin composition to the imidization of the resin composition has a residual stress of 25 MPa or less when the film thickness is 10 μm.

[22] A resin film which is a cured product of the resin composition according to any one of [19] to [21].

[23] A method of producing a resin film, comprising the steps of: developing a resin composition according to any one of [19] to [21] on a surface of a support; and performing the support and the resin composition Heating, the resin precursor contained in the resin composition is imidized to form a resin film; and the resin film is peeled off from the support.

[24] A laminated body comprising a support and a resin film formed on the surface of the support as a cured product of the resin composition according to any one of [19] to [21].

[25] A method of producing a laminate comprising the steps of: developing a resin composition according to any one of [19] to [21] on a surface of a support; and performing the support and the resin composition By heating, the resin precursor contained in the resin composition is imidized to form a resin film, whereby a laminate including the support and the resin film is obtained.

[26] A polyimide resin film which is used by a user for producing a display substrate and has an Rth of 20 to 90 nm at a thickness of 20 μm.

[27] A method of manufacturing a display substrate, comprising the steps of: developing a resin composition containing a polyimide precursor on a surface of a support; Heating the support and the resin composition to carry out oxime imidization of the polyimide precursor to form a polyimide film of [26]; forming a component on the polyimide film And peeling the polyimine resin film on which the element is formed from the support.

According to the present invention, it is possible to provide a resin precursor which can provide a transparent resin cured product without a combination of special solvents, and which can provide a low residual stress with an inorganic film and excellent chemical resistance. A cured resin having a small influence on the YI value and the total light transmittance caused by the oxygen concentration in the curing step.

Hereinafter, an exemplary embodiment (hereinafter, simply referred to as "embodiment") of the present invention will be described in detail. The present invention is not limited to the embodiments described below, and various modifications can be made without departing from the spirit and scope of the invention. In addition, it should be noted that the number of repetitions of the structural unit in the formula of the present disclosure means only the number of structural units which may be included in the entire resin precursor as long as it is not specifically described, and therefore does not mean a specific bonding pattern such as a block structure. . Further, the characteristic values described in the present disclosure mean the values measured by the method disclosed in the item of [Example] or the method understood by the operator in the same manner unless otherwise specified.

<Resin precursor>

The resin precursor system according to the embodiment of the present invention obtains a polymerization component containing an amine group and an amine group-reactive group, and the polymerization component contains a group having two or more selected from the group consisting of an amine group and an amine group. a polyvalent compound comprising a mercapto group-containing compound comprising a diamine represented by the following formula (1):

The resin precursor has a structure represented by the following formula (2):

In the formula, a plurality of R ₃ and R ₄ are each independently a one-carbon organic group having 1 to 20 carbon atoms, and h is an integer of 3 to 200, and the amount of the compound containing a mercapto group is The total mass basis is 6 mass% to 25% by mass.

The polymerization component contains an amine group and an amine group reactive group. The polymerization component contains a polyvalent compound having two or more groups selected from the group consisting of an amine group and an amine group. For example, the polymerization component may be a mixture of a polyvalent compound having an amine group and a polyvalent compound having an amine group reactive group, or may contain a polyvalent compound containing both an amine group and an amine group reactive group, or may be such a combination.

In the present disclosure, the term "amino-reactive group" means a group having reactivity with an amine group. Examples of the amino group-reactive group include an acid group (for example, a carboxyl group, an acid anhydride group, a substituted carboxyl group (for example, an acid ester group or a fluorenyl group)), a hydroxyl group, an epoxy group, and a fluorenyl group. Examples of the acid group-containing compound include dicarboxylic acids, tricarboxylic acids, tetracarboxylic acids, acid dianhydrides, acid esters, and hydrazine chlorides of the carboxylic acids. Therefore, the resin precursor of the present embodiment may be a poly Amine precursor. In a typical aspect, the amino group-reactive group contains at least one selected from the group consisting of a carboxyl group, a substituted carboxyl group, and an acid anhydride group. In a preferred embodiment, the amine-based reactive group is one or more selected from the group consisting of a carboxyl group, a substituted carboxyl group, and an acid anhydride group.

The polyvalent compound contains at least the diamine represented by the formula (1). The compound represented by the formula (1) may be, for example, selected from the group consisting of 4,4-(diaminodiphenyl)fluorene (hereinafter, also referred to as 4,4-DAS), and 3,4-diaminodiphenyl. One or more of the group consisting of 碸) (hereinafter, also referred to as 3,4-DAS) and 3,3-(diaminodiphenyl)anthracene (hereinafter, also referred to as 3,3-DAS) .

At least one of the plurality of compounds is a thiol group-containing compound. The structure represented by the formula (2) is derived from a compound containing a mercapto group. The amount of the thiol group-containing compound is 6% by mass to 25% by mass based on the mass of the multicomponent compound (hereinafter, the mass fraction is also referred to as the concentration of the thiol group-containing monomer). When the concentration of the monomer having a mercapto group is 6% by mass or more, the effect of reducing the stress generated between the resin film and the inorganic film or the effect of lowering the yellowness is sufficiently obtained, and is preferably 7 mass%. The above is more preferably 8% by mass or more, and still more preferably 10% by mass or more. On the other hand, when the concentration of the monomer having a mercapto group is 25% by mass or less, the obtained polyfluorene imide does not cause white turbidity, transparency, yellowness, and good heat resistance. Advantageously, it is preferably 22% by mass or less, and more preferably 20% by mass or less. The concentration of the monomer containing a mercapto group is preferably 10 mass from the viewpoint of improving chemical resistance, YI value, total light transmittance, birefringence, residual stress, and oxygen dependency of optical characteristics. % or more and 20% by mass or less.

In the formula (2), a plurality of R ₃ and R ₄ are each independently a monovalent organic group having 1 to 20 carbon atoms. Examples of the one-valent organic group having 1 to 20 carbon atoms include a monovalent hydrocarbon group having 1 to 20 carbon atoms, an amine group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, and an epoxy group.

Examples of the one-valent hydrocarbon group having 1 to 20 carbon atoms include an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, and an aryl group having 6 to 20 carbon atoms. The alkyl group having 1 to 20 carbon atoms is preferably an alkyl group having 1 to 10 carbon atoms from the viewpoint of heat resistance and residual stress, and specific examples thereof include a methyl group, an ethyl group, a propyl group and an isopropyl group. Base, butyl, isobutyl, tert-butyl, pentyl, Heji and so on. The cycloalkyl group having 3 to 20 carbon atoms is preferably a cycloalkyl group having 3 to 10 carbon atoms, and specific examples thereof include a cyclopentyl group and a cyclohexyl group. The aryl group having 6 to 20 carbon atoms is preferably an aryl group having 6 to 12 carbon atoms, and specific examples thereof include a phenyl group, a tolyl group, and a naphthyl group.

The amine group having 1 to 20 carbon atoms may, for example, be an amine group or a substituted amino group (for example, a bis(trialkyldecyl)amino group).

Examples of the monovalent alkoxy group having 1 to 20 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, a phenoxy group, a propyleneoxy group, a cyclohexyloxy group, and the like. .

In the formula (2), when a plurality of R ₃ and R ₄ are each independently a monovalent aliphatic hydrocarbon group having 1 to 3 carbon atoms or a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms, The polyimide film is preferred from the viewpoint of high heat resistance and low residual stress. From this point of view, the one-valent aliphatic hydrocarbon group having 1 to 3 carbon atoms is preferably a methyl group, and the aromatic group having 6 to 10 carbon atoms is preferably a phenyl group.

h in the general formula (2) is an integer of 3 to 200, preferably an integer of 10 to 200, more preferably an integer of 20 to 150, further preferably an integer of 30 to 100, and particularly preferably 35 to 80. Integer. When h is 2 or less, there is a case where the residual stress of the polyimine obtained by the resin precursor disclosed herein is deteriorated (i.e., increased), and if h exceeds 200, there is a case where a varnish containing a resin precursor and a solvent is prepared. There is a problem that the varnish is cloudy or the mechanical strength of the polyimide is lowered.

In the resin precursor of the present embodiment, the thiol group-containing compound preferably contains a polyfluorene oxide compound represented by the following formula (3):

In the formula, a plurality of R ₂ are independently a single bond or a divalent organic group having 1 to 20 carbon atoms, and R ₃ and R ₄ are each independently a one-carbon organic group having 1 to 20 carbon atoms, and a plurality of organic groups may exist. R _{5 is} independently a monovalent organic group having 1 to 20 carbon atoms, and L ₁ , L ₂ and L ₃ are each independently an amine group, an isocyanate group, a carboxyl group, an acid anhydride group, an acid ester group, a fluorenyl group, a hydroxyl group, and a ring. An oxy or fluorenyl group, j is an integer from 3 to 200, and k is an integer from 0 to 197}. In a preferred embodiment, the thiol-containing compound is a polyfluorene oxide compound represented by the formula (3).

Examples of the divalent organic group having 1 to 20 carbon atoms in R ₂ include a methylene group, an alkylene group having 2 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, and a carbon number of 6 to 20 Aryl and the like. The alkylene group having 2 to 20 carbon atoms is preferably an alkylene group having 2 to 10 carbon atoms from the viewpoint of heat resistance, residual stress, and cost, and examples thereof include a dimethylene group, a trimethylene group, and a tetraalkyl group. Methylene, pentamethylene, hexamethylene and the like. As the cycloalkylene group having 3 to 20 carbon atoms, from the above viewpoint, a cycloalkyl group having 3 to 10 carbon atoms is preferred, and examples thereof include a cyclobutyl group, a cyclopentylene group, a cyclohexylene group, and a stretching group. Cycloheptyl and the like. Among them, from the above viewpoints, a divalent aliphatic hydrocarbon group having 3 to 20 carbon atoms is preferred. In the above viewpoint, the aromatic group having 3 to 20 carbon atoms is preferable, and examples thereof include a stretching phenyl group and a stretching naphthyl group.

, The same as in the general formula (3) R ₃ and R ₃ and R meaning as R in the general formula (2) in ₄ of ₄ of the same preferred aspect of the above described general formula (2) of the. Further, R ₅ is a one-valent organic group having 1 to 20 carbon atoms, that is, the meaning is the same as R ₃ and R ₄ , and the preferred embodiment is the same as R ₃ and R ₄ .

In the formula (3), L ₁ , L ₂ and L ₃ are each independently an amine group, an isocyanate group, a carboxyl group, an acid anhydride group, an acid ester group, a hydrazine halide group, a hydroxyl group, an epoxy group or a fluorenyl group.

The amine group may be substituted, and examples thereof include a bis(trialkyldecyl)amino group and the like. Specific examples of the compound represented by the formula (3) in which L ₁ , L ₂ and L ₃ are an amine group include a two-terminal amine-modified methylphenyl polyfluorene (for example, X22- manufactured by Shin-Etsu Chemical Co., Ltd.) 1660B-3 (number average molecular weight 4,400) and X22-9409 (number average molecular weight 1,300)), both terminal amine-modified dimethyl polyfluorene (for example, X22-161A (quantitative average molecular weight 1,600) manufactured by Shin-Etsu Chemical Co., Ltd., X22-161B (number average molecular weight 3,000) and KF8012 (quantitative average molecular weight 4,400); BY16-835U (quantitative average molecular weight 900) manufactured by Dow Corning Toray; Silaplane FM3311 manufactured by Chisso Corporation (quantitative average molecular weight 1000 ))Wait.

Specific examples of the compound in which L ₁ , L ₂ and L ₃ are isocyanate groups include isocyanate-modified polyfluorene obtained by reacting the above-mentioned two terminal amino group-modified polyfluorene oxides with a carbonium chloride compound.

Specific examples of the compound in which L ₁ , L ₂ and L ₃ are a carboxyl group include X22-162C (quantitative average molecular weight: 4,600) of Shin-Etsu Chemical Co., Ltd., BY16-880 (quantitative average molecular weight of 6,600) manufactured by Toray Dow Corning, and the like.

Specific examples of the compound in which L ₁ , L ₂ and L ₃ are an acid anhydride group include the following formula:

At least one of the thiol compounds and the like represented by the group.

Specific examples of the compound in which L ₁ , L ₂ and L ₃ are an acid anhydride group include X22-168AS (manufactured by Shin-Etsu Chemical Co., Ltd., number average molecular weight: 1,000), X22-168A (manufactured by Shin-Etsu Chemical Co., Ltd., number average molecular weight: 2,000), X22- 168B (manufactured by Shin-Etsu Chemical Co., Ltd., number average molecular weight 3,200), X22-168-P5-8 (manufactured by Shin-Etsu Chemical Co., Ltd., number average molecular weight 4,200), DMS-Z21 (manufactured by Gelest Corporation, number average molecular weight 600-800), and the like.

Specific examples of the compound in which L ₁ , L ₂ and L ₃ are an acid ester group include a compound obtained by reacting a compound in which L ₁ , L ₂ and L ₃ are a carboxyl group or an acid anhydride group with an alcohol.

Specific examples of the compound in which L ₁ , L ₂ and L ₃ are a fluorenyl halide group include a carboxylic acid chloride, a carboxylic acid fluoride, a carboxylic acid bromide, and a carboxylic acid iodide.

Specific examples of the compound in which L ₁ , L ₂ and L ₃ are a hydroxyl group include KF-6000 (manufactured by Shin-Etsu Chemical Co., Ltd., number average molecular weight 900), KF-6001 (manufactured by Shin-Etsu Chemical Co., Ltd., number average molecular weight 1,800), KF-6002 (manufactured by Shin-Etsu Chemical Co., Ltd., number average molecular weight 3,200), KF-6003 (manufactured by Shin-Etsu Chemical Co., Ltd., number average molecular weight 5,000). The compound having a hydroxyl group is considered to react with a compound having a carboxyl group or an acid anhydride group.

Specific examples of the compound in which L ₁ , L ₂ and L ₃ are an epoxy group include X22-163 (manufactured by Shin-Etsu Chemical Co., Ltd., number average molecular weight: 400) and KF-105 (manufactured by Shin-Etsu Chemical Co., Ltd.). A number average molecular weight of 980), X22-163A (manufactured by Shin-Etsu Chemical Co., Ltd., number average molecular weight 2,000), X22-163B (manufactured by Shin-Etsu Chemical Co., Ltd., number average molecular weight 3,500), X22-163C (manufactured by Shin-Etsu Chemical Co., Ltd., number average molecular weight: 5,400); Terminal alicyclic epoxy type X22-169AS (manufactured by Shin-Etsu Chemical Co., Ltd., number average molecular weight 1,000), X22-169B (manufactured by Shin-Etsu Chemical Co., Ltd., number average molecular weight 3,400); X22-9002 as a side chain two-end epoxy type (Shin-Etsu Chemically produced, functional group equivalent weight 5,000 g / mol); The compound having an epoxy group is considered to react with the diamine.

Specific examples of the compound in which L ₁ , L ₂ and L ₃ are a mercapto group include X22-167B (manufactured by Shin-Etsu Chemical Co., Ltd., number average molecular weight: 3,400), X22-167C (manufactured by Shin-Etsu Chemical Co., Ltd., number average molecular weight: 4,600). The compound having a mercapto group is considered to react with a compound having a carboxyl group or an acid anhydride group.

L ₁ , L ₂ and L ₃ are preferably each independently an amine group or an acid anhydride group from the viewpoint of improving the molecular weight of the resin precursor or the heat resistance of the obtained polyimine, thereby avoiding inclusion. From the viewpoint of the white turbidity of the resin precursor and the solvent varnish or the viewpoint of cost, it is more preferable to independently form an amine group.

Alternatively, from the viewpoint of avoiding the white turbidity of the varnish containing the resin precursor and the solvent, or the cost, it is preferred that L ₁ and L ₂ are each independently an amine group or an acid anhydride group, and k is 0. In this case, it is more preferred that both L ₁ and L ₂ are an amine group.

In the general formula (3), the preferred aspect of j is the same as the above description of h in the general formula (2). In the formula (3), k is an integer of 0 to 197, preferably 0 to 100, further preferably 0 to 50, and particularly preferably 0 to 25. When k exceeds 197, there is a case where the varnish causes problems such as white turbidity when a varnish containing a resin precursor and a solvent is prepared. When k is 0, it is preferable from the viewpoint of the improvement of the molecular weight of the resin precursor or the heat resistance of the obtained polyimide. In the case where k is 0, it is advantageous that j is from 3 to 200 from the viewpoint of the improvement of the molecular weight of the resin precursor or the heat resistance of the obtained polyimide.

In a preferred embodiment, in the various formulas of the present disclosure, R ₃ and R ₄ are each independently a carbon number of 1 to 3, a monovalent aliphatic hydrocarbon group, or a carbon number of 6 in terms of residual stress and cost. ~10 one-valent aromatic hydrocarbon group. Alternatively, in each of the formulas of the present disclosure, a part of R ₃ and R ₄ is preferably a phenyl group from the viewpoint of heat resistance and residual stress.

In a preferred aspect, the multicomponent compound comprises a tetracarboxylic dianhydride and a diamine. In a preferred aspect, the multicomponent compound comprises a tetracarboxylic dianhydride, a dicarboxylic acid, and a diamine.

<tetracarboxylic dianhydride>

The tetracarboxylic dianhydride as an example of the polyvalent compound contained in the polymerization raw material is preferably selected from the group consisting of a carbon number of 8 to 36 in terms of a decrease in the YI value and a total light transmittance. A compound of a tetracarboxylic dianhydride and an alicyclic tetracarboxylic dianhydride having a carbon number of 6 to 36.

More specifically, 4,4'-(hexafluoroisopropylidene)diphthalic anhydride (hereinafter also referred to as 6FDA), 5-(2,5-di-side oxytetrahydro-3- Furyl)-3-methyl-cyclohexene-1,2 dicarboxylic anhydride, pyromellitic dianhydride (hereinafter also referred to as PMDA), 1,2,3,4-benzenetetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride (hereinafter also referred to as BTDA), 2,2',3,3'-benzophenonetetracarboxylic dianhydride, 3, 3',4,4'-biphenyltetracarboxylic dianhydride (hereinafter also referred to as BPDA), 3,3',4,4'-diphenylphosphonium tetracarboxylic dianhydride (hereinafter also referred to as DSDA) ), 2,2',3,3'-biphenyltetracarboxylic dianhydride, methylene-4,4'-diphthalic dianhydride, 1,1-Asian Base-4,4'-diphthalic dianhydride, 2,2-propylene-4,4'-diphthalic dianhydride, 1,2-extended ethyl-4,4'-di Phthalic acid dianhydride, 1,3-trimethylene-4,4'-diphthalic dianhydride, 1,4-tetramethylene-4,4'-diphthalic dianhydride, 1,5-pentamethylene-4,4'-diphthalic dianhydride, 4,4'-oxydiphthalic dianhydride (hereinafter also referred to as ODPA), thio-4,4 '-Diphthalic dianhydride, sulfonyl-4,4'-diphthalic dianhydride, 1,3-bis(3,4-dicarboxyphenyl)phthalic anhydride, 1,3- Bis(3,4-dicarboxyphenoxy)phthalic anhydride, 1,4-bis(3,4-dicarboxyphenoxy)phthalic anhydride, 1,3-bis[2-(3,4-di) Carboxyphenyl)-2-propyl]benzene dianhydride, 1,4-bis[2-(3,4-dicarboxyphenyl)-2-propyl]benzene dianhydride, bis[3-(3,4 -Dicarboxyphenoxy)phenyl]methane dianhydride, bis[4-(3,4-dicarboxyphenoxy)phenyl]methane dianhydride, 2,2-bis[3-(3,4-di Carboxyphenoxy)phenyl]propane dianhydride, 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride (hereinafter also referred to as BPADA), double (3, 4-Dicarboxyphenoxy)dimethyl phthalane dianhydride, 1,3-bis(3,4-dicarboxyphenyl)-1,1,3,3-tetramethyldioxane Anhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 3,4 , 9,10-fluorene tetracarboxylic dianhydride, 2,3,6,7-nonanetetracarboxylic dianhydride, 1,2,7,8-phenanthrenetetracarboxylic dianhydride, ethyltetracarboxylic dianhydride 1,2,3,4-butanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride (hereinafter also referred to as CBDA), cyclopentane tetracarboxylic dianhydride Cyclohexane-1,2,3,4-tetracarboxylic dianhydride, cyclohexane-1,2,4,5-tetracarboxylic dianhydride (hereinafter, referred to as CHDA), 3,3', 4 , 4'-bicyclohexyltetracarboxylic dianhydride, carbonyl-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, methylene-4,4'-bis(cyclohexane -1,2-dicarboxylic acid) dianhydride, 1,2-extended ethyl-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, 1,1-ethylene- 4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, 2,2-propylene-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) Anhydride, oxy-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, thio-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) Anhydride, sulfonyl-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, bicyclo[2,2,2]-7-octene-2,3,5,6- Tetracarboxylic dianhydride, rel-[1S,5R,6R]-3-oxabicyclo[3,2,1]octane-2,4-dione-6-spiro-3'-(tetrahydrofuran -2',5'-dione), 4-(2,5-di-oxo-tetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride, B Glycol-bis-(3,4-dicarboxylic anhydride phenyl)ether, 4,4'-biphenylbis(trimellitic acid monoester anhydride) (hereinafter, also referred to as TAHQ), 9,9'-bis(3,4-dicarboxyphenyl)ruthenium anhydride (hereinafter, also referred to as BPAF).

Among them, BTDA and PMDA are preferred from the viewpoints of reduction in CTE, improvement in chemical resistance, improvement in glass transition temperature (Tg), and improvement in mechanical elongation. Further, from the viewpoints of a decrease in yellowness, a decrease in birefringence, and an increase in mechanical elongation, 6FDA, ODPA, and BPADA are preferable. Further, BPDA is preferred from the viewpoints of reduction in residual stress, decrease in yellowness, decrease in birefringence, improvement in chemical resistance, improvement in Tg, and improvement in mechanical elongation. Further, from the viewpoint of a decrease in residual stress and a decrease in yellowness, CHDA is preferred. Among these, it is preferable to exhibit high chemical resistance and high Tg from the viewpoints of high chemical resistance, reduction in residual stress, decrease in yellowness, decrease in birefringence, and improvement in total light transmittance. BPDA with a strong CTE structure and a tetracarboxylic dianhydride which is lower in yellowness and lower birefringence and selected from the group consisting of 6FDA, ODPA and CHDA.

In addition to the above effects, in terms of high elongation, chemical resistance, and high Young's modulus, the portion derived from BPDA is preferably 20% by mole of the entire portion derived from the acid dianhydride. The above is more preferably 50 mol% or more, further preferably 80 mol% or more, and may be 100%.

<dicarboxylic acid>

Further, in the resin precursor of the present embodiment, in addition to the tetracarboxylic dianhydride, the increase in the so-called mechanical elongation, the increase in the glass transition temperature, and the decrease in the yellowness are not included in the resin precursor. For the purpose of performance, the polyacetamide component is introduced by copolymerization of a dicarboxylic acid, whereby the thermosetting film can also be made into a polyamidoximine. Examples of such a dicarboxylic acid include a dicarboxylic acid having an aromatic ring and an alicyclic dicarboxylic acid, and particularly preferably a carbon number of 8 from the viewpoint of a decrease in YI value and total light transmittance. At least one compound selected from the group consisting of aromatic dicarboxylic acid of ~36 and alicyclic dicarboxylic acid having 6 to 34 carbon atoms. Specific examples thereof include isophthalic acid, terephthalic acid, 4,4'-biphenyldicarboxylic acid, 3,4'-biphenyldicarboxylic acid, 3,3'-biphenyldicarboxylic acid, and 1, 4-naphthalenedicarboxylic acid, 2,3-naphthalene Carboxylic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 4,4'-sulfonyldibenzoic acid, 3,4'-sulfonyldibenzoic acid, 3,3'- Sulfonyl dibenzoic acid, 4,4'-oxydibenzoic acid, 3,4'-oxydibenzoic acid, 3,3'-oxydibenzoic acid, 2,2-bis(4-carboxybenzene Propane, 2,2-bis(3-carboxyphenyl)propane, 2,2'-dimethyl-4,4'-biphenyldicarboxylic acid, 3,3'-dimethyl-4,4 '-Biphenyldicarboxylic acid, 2,2'-dimethyl-3,3'-biphenyldicarboxylic acid, 9,9-bis(4-(4-carboxyphenoxy)phenyl)anthracene, 9 ,9-bis(4-(3-carboxyphenoxy)phenyl)anthracene, 4,4'-bis(4-carboxyphenoxy)biphenyl, 4,4'-bis(3-carboxyphenoxy Biphenyl, 3,4'-bis(4-carboxyphenoxy)biphenyl, 3,4'-bis(3-carboxyphenoxy)biphenyl, 3,3'-bis(4-carboxyphenoxyl) Biphenyl, 3,3'-bis(3-carboxyphenoxy)biphenyl, 4,4'-bis(4-carboxyphenoxy)-para-triphenyl, 4,4'-bis (4- Carboxyphenoxy)-m-triphenyl, 3,4'-bis(4-carboxyphenoxy)-para-triphenyl, 3,3'-bis(4-carboxyphenoxy)-para-triphenyl, 3 , 4'-bis(4-carboxyphenoxy)-m-triphenyl, 3,3'-bis(4-carboxyphenoxy)-m-triphenyl, 4,4'-bis(3-carboxybenzene Oxy)-para-triphenyl, 4,4'-double ( 3-carboxyphenoxy)-m-triphenyl, 3,4'-bis(3-carboxyphenoxy)-para-triphenyl, 3,3'-bis(3-carboxyphenoxy)-para-triphenyl , 3,4'-bis(3-carboxyphenoxy)-m-triphenyl, 3,3'-bis(3-carboxyphenoxy)-m-triphenyl, 1,1-cyclobutanedicarboxylate Acid, 1,4-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 4,4'-benzophenone dicarboxylic acid, 1,3-phenylenediacetic acid, 1,4 - a phenylenediacetic acid derivative and a 5-aminoisophthalic acid derivative described in the specification of International Publication No. 2005/068535. In the case where the dicarboxylic acid is actually copolymerized with the polymer, it may be used in the form of a ruthenium chloride or an active ester derived from sulfonium chloride or the like.

Among these, terephthalic acid is particularly preferable from the viewpoint of a decrease in the YI value and an increase in Tg. In the case where a dicarboxylic acid is used in place of the tetracarboxylic acid, the dicarboxylic acid is preferably 50 mol from the viewpoint of chemical resistance with respect to the entire molar amount of the dicarboxylic acid and the tetracarboxylic acid. Less than the ear.

<Diamine>

The diamine contained in the polymerization component contains the diamine represented by the formula (1). The diamine represented by the formula (1) may constitute, for example, a moiety derived from a diamine of the unit 1 described later. Resin precursor Among the parts derived from the diamine represented by the general formula (1), the preferred yellowness, low birefringence, total light transmittance, and residual residue with the inorganic film are obtained. From the viewpoint of a decrease in stress, a high Tg, and a high breaking strength, it is preferably 20 mol% or more, more preferably 50 mol% or more, and still more preferably 80 mol%, based on the entire diamine-derived portion. %the above.

Further, the diamine may include a diamine having a fluorene-containing group having a divalent number of 2 to 100 (hereinafter also referred to simply as a hydrazine-containing diamine). As the hydrazine-containing diamine, for example, a diamino (poly) decane represented by the following formula (9) is preferred:

{Wherein, presence of a plurality of R ₂ each independently having 3 to 20 carbon atoms of the divalent aliphatic hydrocarbon group or a divalent aromatic group, R ₃ and R ₄ are each independently one of 1 to 20 carbon atoms, a monovalent organic group, l is an integer from 3 to 50}. Such a diamine can constitute, for example, a unit 2 to be described later.

Preferred examples of R ₂ in the above formula (9) include a methylene group, an exoethyl group, a propyl group, a butyl group and a phenyl group. Further, preferred examples of R ₃ and R ₄ in the above formula (9) include a methyl group, an ethyl group, a propyl group, a butyl group, and a phenyl group. More preferably, at least a part thereof is a phenyl group.

Specific examples of the compound represented by the above formula (9) include a two-terminal amine-modified methylphenyl sulfonium oil (manufactured by Shin-Etsu Chemical Co., Ltd.: X22-1660B-3 (number average molecular weight 4400), X22-9409 (quantity Average molecular weight 1300)), two-terminal amine-modified dimethyl polyfluorene (manufactured by Shin-Etsu Chemical Co., Ltd.: X22-161A (number average molecular weight 1600), X22-161B (quantitative average molecular weight 3000), KF8021 (quantitative average molecular weight 4400) ), Toray Road Made by Corning: BY16-835U (number average molecular weight 900), manufactured by Chisso: Silaplane FM3311 (number average molecular weight 1000)). Among these, in terms of improvement in chemical resistance and improvement in Tg, a two-terminal amine-modified methylphenyl oxime oil is particularly preferred.

Further, the diamine may also contain 2,2'-bis(trifluoromethyl)benzidine (hereinafter also referred to as TFMB), 4,4'- (or 3,4'-, 3,3'-, 2 , 4'-) Diaminodiphenyl ether, 4,4'-(or 3,3'-)diaminodiphenylanthracene, 4,4'-(or 3,3'-)diaminodiyl Phenyl sulfide, 4,4'-benzophenone diamine, 3,3'-benzophenone diamine, 4,4'-bis(4-aminophenoxy)phenylhydrazine, 4,4 '-bis(3-aminophenoxy)phenylhydrazine, 4,4'-bis(4-aminophenoxy)biphenyl, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 2,2-bis{4-(4-aminophenoxy)phenyl}propane, 3,3',5,5'-tetramethyl Base-4,4'-diaminodiphenylmethane, 2,2'-bis(4-aminophenyl)propane, 2,2',6,6'-tetramethyl-4,4'-di Aminobiphenyl, 2,2',6,6'-tetrakis(trifluoromethyl)-4,4'-diaminobiphenyl, bis{(4-aminophenyl)-2-propyl} 1,4-Benzene, 9,9-bis(4-aminophenyl)anthracene, 9,9-bis(4-aminophenoxyphenyl)anthracene, 3,3'-dimethylbenzidine, 3,3'-dimethoxybenzidine and 3,5-diaminobenzoic acid and the like are selected from the group consisting of 2,6-diaminopyridine, 2,4-diaminopyridine, bis(4-aminophenyl) -2-propyl)-1,4-benzene, 3,3'-bis(trifluoromethyl)-4,4'-diaminobiphenyl (3,3'-TFDB) 2,2'-bis[3(3-aminophenoxy)phenyl]hexafluoropropane (3-BDAF), 2,2'-bis[4(4-aminophenoxy)phenyl]hexa Fluoropropane (4-BDAF), 2,2'-bis(3-aminophenyl)hexafluoropropane (3,3'-6F) and 2,2'-bis(4-aminophenyl)hexafluoro One or more of the group consisting of propane (4, 4'-6F). These diamines may constitute a moiety derived from a diamine of the unit 3 described later. Among these, 1,4-cyclohexanediamine and TFMB are most preferable from the viewpoint of a decrease in yellowness, a decrease in CTE, and a decrease in YI value.

More preferably, the resin precursor contains the following unit 1 and unit 2.

The unit 1 has at least the structure represented by the following formula (4): [Chem. 14]

In the formula, there are a plurality of R ₁ independently being a hydrogen atom, a carbon number of 1 to 20, a monovalent aliphatic hydrocarbon group or a monovalent aromatic group, and there may be a plurality of X ₁ independently of carbon numbers 4 to 32. a tetravalent organic group, and n is an integer of from 1 to 100}, and the unit 2 has a structure represented by the following formula (5):

In the formula, a plurality of R ₁ are independently a hydrogen atom, a carbon number of 1 to 20, a monovalent aliphatic hydrocarbon group or a monovalent aromatic group, and a plurality of R ₂ are independently 3 to 20 carbon atoms. a valence aliphatic hydrocarbon group or a divalent aromatic group, R ₃ and R ₄ are each independently a one-carbon organic group having 1 to 20 carbon atoms, and a plurality of X ₂ organic groups independently having a carbon number of 4 to 32 may be present. , l is an integer from 3 to 50, and m is an integer from 1 to 100} or a structure represented by the following general formula (6):

In the formula, there are a plurality of R ₁ independently being a hydrogen atom, a carbon number of 1 to 20, a monovalent aliphatic hydrocarbon group or a monovalent aromatic group, and a plurality of R ₃ and R ₄ are independently a carbon number 1~ 20 one-valent organic group, a plurality of R ₈ are independently a trivalent aliphatic hydrocarbon group or a trivalent aromatic group having 3 to 20 carbon atoms, p is an integer of 1 to 100, and q is an integer of 3 to 50 } or both the structure represented by the above formula (5) and the structure represented by the above formula (6).

In the general formulae (4) and (6), the moiety derived from the diamine may be derived, for example, from the group consisting of 4,4-(diaminodiphenyl)fluorene and 3,4-(diaminodiphenyl). And one or more diamines of the group consisting of 3,3-(diaminodiphenyl)fluorene. In the general formulae (4) and (5), the acid anhydride-derived sites are respectively derived from an acid dianhydride having a tetravalent organic group X ₁ (X ₁ is as defined above) and having a tetravalent organic group X ₂ (X _{2 )} Acid dianhydride as defined above). The moiety derived from the diamine in the structure represented by the formula (5) is derived from the diamino (poly) alkane represented by the formula (9).

The unit 1 and the unit 2 are preferably 60 mol% based on the total amount of the acid dianhydride-derived portion of the unit 1 and the unit 2 from the viewpoint of heat resistance, reduction in YI value, and total light transmittance. More preferably, the portion is a combination of the following two portions in an amount of 65 mol% or more, and more preferably 70 mol% or more, and the two portions are selected from the group consisting of pyromellitic dianhydride (PMDA). And one or more sites selected from the group consisting of biphenyltetracarboxylic dianhydride (BPDA), and a source selected from the group consisting of 4,4'-oxydiphthalic dianhydride (ODPA), 4, 4'- (hexafluoroisopropylidene)diphthalic anhydride (6FDA), cyclohexane-1,2,4,5-tetracarboxylic dianhydride (CHDA), 3,3',4,4'-di Phenylhydrazine tetracarboxylic dianhydride (DSDA), 4,4'-biphenyl bis(trimellitic acid monoester anhydride) (TAHQ) and 9,9'-bis(3,4-dicarboxyphenyl)fluorene One or more sites in the group consisting of dianhydride (BPAF).

In the resin precursor of the present embodiment, the total mass of the unit 1 and the unit 2 is preferably from the viewpoint of the total mass of the resin precursor, from the viewpoint of a decrease in the YI value, a decrease in the birefringence, and an increase in the Tg. 30% by mass or more, in terms of reduction of birefringence Further, it is preferably 70% by mass or more. The best is 100% by mass.

Further, in the resin precursor of the present embodiment, the unit 3 having the structure represented by the following general formula (7) may be further contained as long as it does not impair the performance:

In the formula, a plurality of R ₁ are independently a hydrogen atom, a carbon number of 1 to 20, a monovalent aliphatic hydrocarbon group or a monovalent aromatic group, and a plurality of X ₃ may be independently a carbon number of 4 to 32. The divalent organic group may have a plurality of X ₄ independently independently a tetravalent organic group having a carbon number of 4 to 32, and t is an integer of 1 to 100}.

The unit 3 derived from the diamine is derived from a diamine other than a compound selected from the group consisting of 4,4-DAS, 3,4-DAS, 3,3-DAS, and a hydrazine-containing diamine. The structure of the part.

In the unit 3, R _{1 is} preferably a hydrogen atom. Further, X _{3 is} preferably a divalent aromatic group or an alicyclic group from the viewpoint of heat resistance, reduction in YI value, and total light transmittance. Further, X _{4 is} preferably a divalent aromatic group or an alicyclic group from the viewpoint of heat resistance, reduction in YI value, and total light transmittance. Among them, X _{3 is} preferably a residue obtained by removing an amine group from 2,2'-bis(trifluoromethyl)benzidine. The organic groups X ₁ , X ₂ and X ₄ may be the same or different from each other.

The mass ratio of the unit 3 in the resin precursor of the present embodiment is preferably 80% by mass or less based on the total resin structure, from the viewpoint of a decrease in the YI value and the oxygen dependency of the total light transmittance. It is 70% by mass or less.

The resin precursor of the present embodiment is preferably obtained by heat-hardening the resin precursor under an inert gas atmosphere (for example, under a nitrogen or argon atmosphere) at 300 to 500 ° C. The resin obtained by heat-hardening the resin precursor in an inert gas atmosphere at 350 ° C has at least one glass transition temperature in a region of -150 ° C to 0 ° C and at 150 ° C to 380 ° C. At least one glass transition temperature of the region, and no glass transition temperature in a region greater than 0 ° C and less than 150 ° C. The glass transition temperature is present in the region of -150 ° C to 0 ° C and in the region of 150 ° C to 380 ° C, and is preferable from the viewpoint of achieving a good balance between the residual stress and the total light transmittance. From the viewpoint of heat resistance, the glass transition temperature in the region of 150 ° C to 380 ° C is more preferably in the range of 200 to 380 ° C, and more preferably in the region of 250 to 380 ° C. The case where the resin precursor has the block 1 and the block 2 described later is advantageous for forming such a resin precursor.

From the viewpoint of improving heat resistance, the resin precursor of the present embodiment is preferably composed of a block 1 mainly composed of the unit 1 and a block 2 mainly composed of the unit 2. Further, in the resin precursor, the block 1 may also include the above unit 3. The blocks may be alternately bonded in the polymer chain or sequentially bonded.

The block 1 is used in the polyimine obtained by heat-hardening the resin precursor of the present embodiment, and contributes to exhibiting Tg in the range of 150 to 380 °C. Therefore, the block 1 is preferably a block composed only of the above-mentioned unit 1 in the reverse direction, but the unit 3 other than the unit 1 is not excluded insofar as the target Tg can be expressed.

Similarly, the above-mentioned block 2 is used in the polyimine obtained by heat-hardening the resin precursor of the present embodiment, and contributes to exhibiting Tg in the range of -150 to 0 °C. Therefore, the block 2 is preferably a block composed only of the above-mentioned unit 2, but it is not excluded to include a unit other than the unit 2 within a range in which the target Tg can be expressed.

In the resin precursor having the block 1 and the block 2, the sum of the number of repetitions of the unit 1 and the unit 3 in the block 1 is preferably 2 to 500, more preferably 5 to 300, most preferably 10~200. Further, the number of repetitions of the unit 2 in the block 2 is preferably from 1.1 to 300, more preferably from 1.1 to 200, and most preferably from 1.2 to 100, per one molecule. The sum of the number of repetitions of the unit 1 and the unit 3 in the block 1 is 500 or less, and the number of repetitions of the unit 2 in the block 2 is 300 or less, It is preferable that the resin precursor has good solubility in a solvent.

The ratio defined by the sum of the number of repetitions of the unit 1 and the unit 3 in the block 1 divided by the number of repetitions of the unit 2 in the block 2 (hereinafter also referred to as the unit ratio) also depends on the raw materials used. The type or molecular weight, but preferably 0.5 to 100, more preferably 10 to 50. As described above, the polyimine as the cured product of the resin precursor of the block 1 and the block 2 may have an advantage of having a glass transition temperature derived from the block 1 in the region A of 150 ° C to 380 ° C There is a glass transition temperature derived from the block 2 in the region B of -150 ° C to 0 ° C, and there is no glass transition temperature in the region C between the region A and the region B. When the ratio of the above unit is 0.5 or more, the heat resistance of the polyimine resin after curing becomes sufficient, which is preferable. Further, in the case of 100 or less, the residual stress can be lowered, which is preferable.

On the other hand, when a high molecular weight polyoxynitride (specifically, a polyfluorene oxide having an average molecular weight of 3,000 or more) is used as the thiol group-containing compound in the polymerization component, even if the block as described above is not formed The copolymer, the obtained polyimide, can also maintain a high glass transition temperature and exhibit low residual stress with the inorganic film. The reason for this is that the polyfluorene oxide unit itself has a long-chain siloxane structure according to a high molecular weight polyoxynitride compound, and therefore it is considered to have the same function as the above-mentioned block structure. Here, when the polyoxyxene compound has a high molecular weight, the functional group concentration is lowered, so that even if the number of moles fed is small, the high glass transition temperature and the low residual stress can be expressed.

For example, in the case where the high molecular weight polyoxo compound is a diamine, with respect to the resin precursor, the unit 1 derived from the formula (4) derived from (diaminodiphenyl) fluorene is derived from the polyoxyxene In addition to the copolymer of unit 2 of the formula (5) of the amine, there is also a polyamidiene precursor mixture, ie, blended, of the polyimine precursor of unit 1 alone (ie, not copolymerized with unit 2) Things.

Accordingly, the present disclosure also includes a precursor mixture comprising the resin precursor of the above-described embodiment and an additional resin precursor (for example, the above-mentioned unit 1 alone polyimide intermediate precursor). Here, as a specific example of the polyimide precursor precursor of the unit 1 alone, a resin precursor having a structure represented by the following formula (8) is exemplified:

In the formula, a plurality of X ₃ may be independently a tetravalent organic group having a carbon number of 4 to 32, and a plurality of R ₁ are independently a hydrogen atom, a carbon number of 1 to 20, a monovalent aliphatic hydrocarbon group or a Avalent aromatic group, and r is an integer from 1 to 100}.

On the other hand, the high molecular weight polyoxo compound is an example other than the diamine. For example, in the general formula (3), L ₁ , L ₂ and L ₃ are each independently an acid anhydride group, a carboxyl group, an acid ester group or a fluorenyl halide group. a polyoxyl compound of a hydroxyl group, an epoxy group or a mercapto group.

In the case where the polymer component contains a high molecular weight polyoxyxene compound in the resin precursor of the present embodiment, the polyimine which is a cured product of the resin precursor can achieve the following specific characteristics: maintaining a high temperature of 150 ° C to 380 ° C In the state of the glass transition temperature in the region, the residual stress with the inorganic film can be remarkably reduced.

The number average molecular weight of the resin precursor of the present embodiment is preferably from 3,000 to 1,000,000, more preferably from 5,000 to 500,000, further preferably from 7,000 to 300,000, and particularly preferably from 10,000 to 250,000. From the viewpoint of obtaining heat resistance or strength (e.g., strong elongation), the molecular weight is preferably 3,000 or more, and the viewpoint of solubility in a solvent is favorably obtained, and the coating layer can be coated without penetration during processing. From the viewpoint of the desired film thickness, it is preferably 1,000,000 or less. From the viewpoint of obtaining a high mechanical elongation, the molecular weight is preferably 50,000 or more. In the present disclosure, the number average molecular weight is determined by gel permeation chromatography. The value obtained from the standard polystyrene conversion.

In a preferred embodiment, a portion of the resin precursor can also be ruthenium imidized.

The resin precursor of the present embodiment can form heat resistance as a display manufacturing step capable of withstanding a TFT element device on a colorless transparent polyimide substrate, and has a glass transition temperature of 150 ° C to 380 ° C on a high temperature side, and the film thickness is A polyimine resin having a residual stress between the inorganic film and a thickness of 25 MPa at 10 μm. Further, in a more preferable aspect, the resin precursor can form a polyimide resin having a glass transition temperature of 240 ° C to 380 ° C and a film thickness of 10 μm and a residual stress of 20 MPa or less with the inorganic film. In the case of the polyimide resin, when the glass transition temperature is present at -150 to 0 ° C, the temperature is below room temperature, so that the heat resistance required in the actual display manufacturing step is not affected.

Further, in a preferred embodiment, the resin precursor has the following characteristics.

After the solution obtained by dissolving the resin precursor in a solvent (for example, N-methyl-2-pyrrolidone) is spread on the surface of the support, the solution is subjected to a nitrogen atmosphere at 300 to 500 ° C (for example, 350). In the resin obtained by subjecting the resin precursor to imidization by heating (for example, 1 hour) at a temperature of ° C), the yellowness at a film thickness of 20 μm is 7 or less.

After the solution obtained by dissolving the resin precursor in a solvent (for example, N-methyl-2-pyrrolidone) is spread on the surface of the support, the solution is subjected to a nitrogen atmosphere at 300 to 500 ° C (for example, 350). In the resin obtained by subjecting the resin precursor to imidization by heating (for example, 1 hour) at ° C), the residual stress at a film thickness of 10 μm is 25 MPa or less.

<Manufacture of Resin Precursor>

Next, a method of synthesizing the resin precursor of the present embodiment will be described. For example, when the resin precursor of the present embodiment is composed of two blocks such as the above-described block 1 and block 2, a polyimide precursor precursor corresponding to each block is separately prepared in advance, and then The resin precursor of the present embodiment can be obtained by mixing the two and supplying them to a condensation reaction. Here, in the case where the terminal group of the polyamidene precursor of one of the blocks is set to a carboxylic acid in such a manner that the two blocks can be supplied to the condensation reaction, The terminal group of the other polyimide precursor of the block becomes an amine group treatment or the like, and the molar ratio of each raw material, for example, the molar ratio of the tetracarboxylic dianhydride to the diamine, is adjusted. In this method, a better polyimine precursor having a complete blockiness can be synthesized.

On the other hand, the tetracarboxylic dianhydride which is a polymerization raw material is common between the block 1 and the block 2, and an aromatic diamine is used as a raw material of the block 1, and a highly reactive hydrazine-containing diamine is used as the embedding. In the case of the raw material of the stage 2, there is a case where a synthesis method using a poor reactivity of the diamine can be used. For example, an aromatic diamine and a hydrazine-containing diamine are simultaneously added to a tetracarboxylic dianhydride prepared in advance, and a condensation reaction is provided, whereby a polyimide intermediate having a certain degree of block property can be produced. . In this method, a block polyimine precursor having a complete block property cannot be synthesized, but a blocky polyimine precursor can be synthesized. Here, the term "blocking property" means that the glass transition temperature corresponding to each block is observed in the polyimide resin after heat curing, for example, each of the above-mentioned region A and region B of the polyimide resin. Respectively derived from a group selected from the group consisting of 4,4-(diaminodiphenyl)anthracene, 3,4-(diaminodiphenyl)anthracene and 3,3-(diaminodiphenyl)anthracene. The glass transition temperature of the block 1 of one or more of the polycondensate of the tetracarboxylic anhydride and the block 2 derived from the block 2 of the polycondensate of the diamine and the tetracarboxylic anhydride.

As described above, in the resin precursor of the present embodiment, it is advantageous that the polyimide resin obtained by heat-hardening the resin precursor is confirmed in the region A on the high temperature side and the region B on the low temperature side. The degree of blockage of the glass transition temperature, but this advantage can be obtained even if the polyimide resin does not have a complete block property. Further, the above-described advantages of the resin precursor having the blocks 1 and 2 may include units other than the block 1 and the block 2 as long as the glass transition temperature is confirmed in the region C between the region A and the region B. .

Further, N,N-dimethylformamide dimethyl acetal or N,N-dimethylformamide diethyl acetal is added to the polyamic acid as described above and heated. Part or all of the carboxylic acid is esterified, whereby the viscosity stability of the solution containing the resin precursor and the solvent at room temperature can be improved. The ester modified polyaminic acid can also be obtained by other means: The tetracarboxylic acid anhydride is previously reacted with one equivalent of the monohydric alcohol relative to the acid anhydride group, and then reacted with a dehydrating condensing agent such as sulfinium chloride or dicyclohexylcarbodiimide to carry out a condensation reaction with the diamine.

<Resin composition>

Another aspect of the present invention provides a resin composition comprising the above resin precursor or precursor mixture and a solvent. The resin composition is typically a varnish.

More preferably, the resin composition can be produced by dissolving a carboxylic acid component and a diamine component in a solvent, for example, an organic solvent, to produce a polyamine containing one aspect as a resin precursor. A polyaminic acid solution of an acid and a solvent. Here, the conditions at the time of the reaction are not particularly limited, but, for example, the reaction temperature is -20 to 150 ° C, and the reaction time is 2 to 48 hours. In order to sufficiently carry out the reaction of the mercapto group-containing compound, it is preferably heated at about 120 ° C for about 30 minutes. Further, in the reaction, an inert gas atmosphere such as argon gas or nitrogen gas is preferred.

Further, the solvent is not particularly limited as long as it dissolves the solvent of polylysine. As a known reaction solvent, it is useful to be selected from the group consisting of diethylene glycol dimethyl ether (DMDG), m-cresol, N-methyl-2-pyrrolidone (NMP), dimethylformamide (DMF), and Methylacetamide (DMAc), dimethyl hydrazine (DMSO), acetone, diethyl acetate, Equamide M100 (trade name: manufactured by Idemitsu Kosan Co., Ltd.) and Equamide B100 (trade name: Idemitsu Kosan Co., Ltd.) One or more kinds of polar solvents in the manufacture). Among them, preferred are NMP, DMAc, Equamide M100 and Equamide B100. Further, a low boiling point solution such as tetrahydrofuran (THF) or chloroform or a low absorption solvent such as γ-butyrolactone may be used.

In the resin composition of the present invention, when a device such as a TFT is formed from the obtained polyimide, it is preferably contained in an amount of 100% by mass based on the resin precursor in order to impart sufficient adhesion to the support. The alkoxydecane compound has a composition of 0.01 to 2% by mass.

The content of the alkoxydecane compound is 0.01% by mass or more based on 100% by mass of the resin precursor, whereby good adhesion to the support can be obtained, and in addition, the resin combination From the viewpoint of storage stability of the material, the content of the alkoxydecane compound is preferably 2% by mass or less. The content of the alkoxydecane compound is more preferably 0.02 to 2% by mass, still more preferably 0.05 to 1% by mass, still more preferably 0.05 to 0.5% by mass, still more preferably 0.1 to 0.5% by mass, based on the resin precursor. .

Examples of the alkoxydecane compound include 3-ureidopropyltriethoxydecane, bis(2-hydroxyethyl)-3-aminopropyltriethoxydecane, and 3-glycidoxypropyl group. Trimethoxydecane, phenyltrimethoxydecane, γ-aminopropyltriethoxydecane, γ-aminopropyltrimethoxydecane, γ-aminopropyltripropoxydecane, γ-amine Propyl tributoxy decane, γ-aminoethyl triethoxy decane, γ-aminoethyl trimethoxy decane, γ-aminoethyl tripropoxy decane, γ-aminoethyl Tributoxy decane, γ-aminobutyl triethoxy decane, γ-aminobutyl trimethoxy decane, γ-aminobutyl tripropoxy decane, γ-aminobutyl tributoxide Further, these may be used in combination of two or more kinds.

After the varnish is produced, the solution is heated at 130 to 200 ° C for 5 minutes to 2 hours, whereby one part of the polymer may be dehydrated and imidized to such an extent that the polymer does not cause precipitation. The sulfhydrylation rate can be controlled by temperature and time control. By performing partial oxime imidization, the viscosity stability of the resin precursor solution at room temperature storage can be improved. The range of the ruthenium iodide ratio is preferably from 5% to 70% from the viewpoints of the solubility of the resin precursor to the solution and the storage stability of the solution.

Further, in a preferred embodiment, the resin composition has the following characteristics.

After the resin composition is developed on the surface of the support, the resin composition is heated at 300 ° C to 500 ° C under a nitrogen atmosphere (or by heating at 350 ° C in a nitrogen atmosphere). When the resin obtained by the ruthenium imidization of the resin precursor contained in the resin composition has a film thickness of 20 μm, the yellowness is 7 or less.

After the resin composition is developed on the surface of the support, the resin composition is heated at 300 ° C to 500 ° C under a nitrogen atmosphere (or by heating at 350 ° C in a nitrogen atmosphere). The resin precursor contained in the resin composition is subjected to quinone imine The residual stress when the film thickness of the resin obtained by the resin is 10 μm is 25 MPa or less.

<Resin film>

According to another aspect of the invention, there is provided a resin film of a cured product of the resin precursor, a resin film of the cured product of the precursor mixture, or a resin film of a cured product of the resin composition.

Moreover, another aspect of the present invention provides a method for producing a resin film, comprising the steps of: developing the resin composition on a surface of a support; and heating the support and the resin composition to cause the resin The resin precursor contained in the composition is imidized to form a resin film; and the resin film is peeled off from the support.

In a preferred embodiment of the method for producing a resin film, as the resin composition, a polyaminic acid solution obtained by dissolving an acid dianhydride component and a diamine component in an organic solvent and performing a reaction can be used.

Here, the support is, for example, an inorganic substrate such as a glass substrate such as an alkali-free glass substrate, but is not particularly limited.

More specifically, the resin composition is developed on an adhesive layer formed on the main surface of the inorganic substrate, dried, and cured at an inert gas atmosphere at a temperature of 300 to 500 ° C to form a resin. membrane. Finally, the resin film was peeled off from the support.

Here, as a developing method, a well-known coating method of spin coating, slit coating, and blade coating is mentioned, for example. Further, in the heat treatment, after the polyamic acid solution is developed on the adhesive layer, the heat treatment is performed for 1 minute to 300 minutes at a temperature of 300 ° C or lower, mainly for desolvation, and further, in an inert gas atmosphere such as nitrogen. The resin precursor is subjected to polyazylation at a temperature of 300 ° C to 550 ° C for 1 minute to 300 minutes. In the case of the production of the previously colorless transparent polyimide film, the oxygen concentration in the oven must be managed to 100 ppm from the viewpoint of the reduction of the YI value and the total light transmittance. Next, according to the resin precursor in the present embodiment, management of 500 ppm or less is sufficient. The oxygen concentration is preferably 1000 ppm or less from the viewpoint of a decrease in the YI value and an increase in the total light transmittance.

Further, the thickness of the resin film of the present embodiment is not particularly limited, but is preferably in the range of 10 to 200 μm, more preferably 10 to 50 μm.

The resin film of the present embodiment preferably has a yellowness of 7 or less when the film thickness is 20 μm. Further, it is preferable that the residual stress at a film thickness of 10 μm is 25 MPa or less. In particular, it is more preferable that the yellowness at a film thickness of 20 μm is 7 or less, and the residual stress at a film thickness of 10 μm is 25 MPa or less. This property is satisfactorily achieved, for example, by subjecting the resin precursor of the present invention to imidization at 300 ° C to 500 ° C, more specifically at 350 ° C under a nitrogen atmosphere.

<Laminated body>

Another aspect of the present invention provides a laminate comprising a support and a resin film formed on the surface of the support as a cured product of the resin composition.

Still another aspect of the present invention provides a method for producing a laminate comprising the steps of: developing the resin composition on a surface of a support; and heating the support and the resin composition to cause the resin The resin precursor contained in the composition is imidized to form a resin film, whereby a laminate including the support and the resin film is obtained.

Such a laminated system can be produced, for example, by a resin film formed in the same manner as the above-described method for producing a resin film, which is not peeled off from the support.

This laminate is used, for example, in the manufacture of flexible devices. More specifically, a semiconductor device is formed on a polyimide film, and thereafter, the support is peeled off to obtain a flexible device including a flexible transparent substrate including a polyimide film.

Therefore, another aspect of the present invention provides a resin precursor comprising the above or the above Flexible device material for the precursor mixture.

As described above, the resin precursor of the present embodiment has a specific structure, whereby a resin film which does not cause white turbidity can be formed without requiring a combination of special solvents. Further, the yellowness (YI value) and total light transmittance of the obtained resin film are less dependent on the oxygen concentration at the time of curing. Further, the residual stress generated between the resin film and the inorganic film is low, and it has a practical glass transition temperature which can withstand the TFT production step, is excellent in mechanical properties, and has chemical resistance capable of withstanding the photolithography step. Therefore, the resin precursor is suitable for use in a transparent substrate of a flexible display.

In the case where a flexible display is formed in detail, a flexible substrate is formed on the glass substrate as a support, and a TFT or the like is formed thereon. The step of forming the TFT on the substrate is typically carried out at a wide temperature of 150 to 650 ° C, but in order to achieve the actual required performance, an inorganic material is mainly used at a temperature of about 250 ° C to 350 ° C to form a TFT-IGZO ( InGaZnO) oxide semiconductor or TFT (a-Si-TFT, poly-Si-TFT).

In this case, when the residual stress generated between the flexible substrate and the polyimide film is high, the glass substrate is warped or collapsed when the film is expanded in the high-temperature TFT step, and shrinkage occurs during cooling at room temperature. Problems such as peeling of the flexible substrate from the glass substrate. Generally, the glass substrate has a thermal expansion coefficient smaller than that of the resin, so that residual stress is generated between the flexible substrate and the flexible substrate. In view of this, the resin film of the present embodiment preferably has a residual stress of 25 MPa or less between the resin film and the glass based on the thickness of the film of 10 μm.

Further, the resin film of the present embodiment preferably has a yellowness of 7 or less and a yellowness of 7 or less, and a transmittance of 550 nm when the transmittance is measured by an ultraviolet spectrophotometer based on a thickness of 20 μm of the film. The rate is over 85%. Moreover, it is advantageous to stably obtain a resin film having a low YI value in the case where the oxygen concentration in the oven used for producing the thermosetting film is small, and it is preferably a thermosetting film when the oxygen concentration is 500 ppm or less. The YI value tends to be stable.

Further, in the resin film of the present embodiment, when the flexible substrate is operated, the breaking strength is excellent, and from the viewpoint of improving the yield, the mechanical elongation is more preferably based on the thickness of the film of 20 μm. More than 30%.

Further, in the resin film of the present embodiment, in order to prevent softening of the resin substrate at the temperature at which the TFT element is produced, the glass transition temperature is preferably 250 ° C or higher.

Further, the resin film of the present embodiment preferably has chemical resistance capable of withstanding the photoresist stripping liquid in the photolithography step used in the production of the TFT element.

Further, the light extraction method of the flexible display includes two types of the top emission mode for extracting light from the surface side of the TFT element and the bottom emission mode for extracting light from the back surface side. In the top emission mode, the TFT element is not hindered, so that it is easy to increase the aperture ratio, and the bottom emission method has the characteristics of easy positioning and easy manufacture. As long as the TFT element is transparent, the aperture ratio can be increased in the bottom emission method. Therefore, it is expected that a bottom emission method which is easy to manufacture can be employed in a large organic EL (Electroluminescence) flexible display. When a resin substrate is used for the colorless transparent resin substrate used in the bottom emission method, the resin substrate comes to the viewing side. Therefore, from the viewpoint of improving the image quality, the optical isotropic property is derived from the thickness direction of the birefringence. The delay (Rth) is low. Further, in the case of the top emission mode, the Rth cannot be required to be low, but from the viewpoint of common use for the two modes, a material having a lower Rth is preferable. Specifically, the film has a thickness of 20 μm, preferably 200 nm or less, more preferably 90 nm or less, further preferably 80 nm or less, and particularly preferably 50 nm or less. When the Rth is 100 nm or less and further 90 nm or less, it not only satisfies the performance of the transparent substrate for a flexible display for use in a top emission type, but also satisfies a transparent substrate for a flexible display for use in a bottom emission type or Performance of an electrode substrate for a touch panel.

Another aspect of the present invention provides a polyimide film which is a user of a display substrate and has an Rth of 20 to 90 nm at a thickness of 20 μm.

Moreover, another aspect of the present invention provides a method of manufacturing a display substrate, which comprises The method comprises the steps of: unrolling a resin composition containing a polyimide precursor on a surface of the support; heating the support and the resin composition to cause the polyimide precursor to be imidized to form The polyimine resin film; forming an element on the polyimide film; and peeling the polyimide film formed with the element from the support.

The resin film of the present embodiment which satisfies the above physical properties is preferably applied to a use which is restricted by the yellow color of the conventional polyimide film, and is particularly preferably used as a colorless transparent substrate for a flexible display. Further, for example, it can be applied to a astigmatic sheet and a coating film in a protective film or a TFT-LCD (for example, an intermediate layer of a TFT-LCD, a gate insulating film, and a liquid crystal alignment film), an ITO substrate for a touch panel, and an intelligent film. A cover glass for a mobile phone is used in the field of requiring colorless transparency and low birefringence, such as a resin substrate. When the polyimine of this embodiment is used as a liquid crystal alignment film, it contributes to an increase in aperture ratio, and a TFT-LCD having a high contrast ratio can be manufactured.

The resin film and the laminated body produced by using the resin precursor of the present embodiment can be preferably used, for example, for producing a semiconductor insulating film, a TFT-LCD insulating film, an electrode protective film, and a flexible device, and particularly preferably used. As a substrate. Here, examples of the flexible device include a flexible display, a flexible solar cell, a flexible touch panel electrode substrate, a flexible illumination, and a flexible battery.

[Examples]

Hereinafter, the present invention will be described in detail based on examples, but these are described for the sake of explanation, and the scope of the present invention is not limited to the following examples.

The various evaluations in the examples and comparative examples are as follows.

(Measurement of weight average molecular weight)

The weight average molecular weight (Mw) was measured by gel permeation chromatography (GPC) under the following conditions. As a solvent, N,N-dimethylformamide (Wako Pure Chemical Industries, Ltd.) Manufactured, used in high performance liquid chromatography), and added 24.8 mmol/L of lithium bromide monohydrate (manufactured by Wako Pure Chemical Industries, Ltd., purity 99.5%) and 63.2 mmol/L of phosphoric acid before the measurement (Wako Pure Chemical Industries Co., Ltd.) Manufactured, used in high performance liquid chromatography. Further, a calibration curve for calculating a weight average molecular weight was prepared using standard polystyrene (manufactured by Tosoh Corporation).

Pipe column: Shodex KD-806M (made by Showa Denko)

Flow rate: 1.0mL/min

Column temperature: 40 ° C

Pump: PU-2080Plus (manufactured by JASCO)

Detector: RI-2031Plus (RI: differential refractometer, manufactured by JASCO)

UV-2075Plus (UV-VIS: UV-visible absorbometer, manufactured by JASCO)

(concentration of monomer containing mercapto group)

The concentration of the monomer containing a mercapto group is determined by the following formula using the respective masses of a mercapto group-containing monomer, a polyvalent carboxylic acid or a derivative thereof, and a diamine compound used in the case of using a synthetic resin precursor.

Concentration (%) of monomer containing mercapto group = mass of monomer containing mercapto group / (monomer mass of mercapto group + mass of polycarboxylic acid or its derivative + mass of diamine compound) × 100

(Production of laminated body and single film)

The resin composition was coated on an alkali-free glass substrate (thickness: 0.7 mm) by a bar coater, and leveled at room temperature for 5 minutes to 10 minutes, and a vertical curing oven (manufactured by Koyo Lindberg Co., Ltd., type) was used. The name VF-2000B) was heated at 140 ° C for 60 minutes, and further heated at 350 ° C for 60 minutes in a nitrogen atmosphere to prepare a laminate. At this time, the oxygen concentration in the hot air oven was adjusted to 50 ppm, 100 ppm, and 500 ppm, respectively, and the YI value and the oxygen concentration dependence of the total light transmittance were observed. The film thickness of the resin composition of the laminate was 20 μm. After curing at 350 ° C (hardening treatment), the laminate was allowed to stand at room temperature for 24 hours, and The resin film was peeled off from the glass to separate the film. The following evaluations other than yellowness and total light transmittance were carried out by adjusting the oxygen concentration in the hot air oven to 100 ppm, and curing the resin film at 350 ° C for 60 minutes.

(Evaluation of tensile elongation)

A resin film having a sample length of 5 × 50 mm and a thickness of 20 μm which was cured at 350 ° C was stretched at a speed of 100 mm/min using a tensile tester (manufactured by A&D Co., Ltd.: RTG-1210) to measure the stretching. Elongation.

(yellowness, total light transmittance and oxygen concentration dependence during curing)

The oxygen concentration in the oven was adjusted to 50 ppm, 100 ppm, and 500 ppm, respectively, and the resin film having a thickness of 20 μm which was cured at 350 ° C was produced by using a D65 light source (Spectrophotometer: SE600) manufactured by Nippon Denshoku Industries Co., Ltd., and yellow was measured. Degree (YI value) and total light transmittance.

(Evaluation of thickness direction retardation (Rth))

A resin film having a thickness of 20 μm which was cured at 350 ° C was measured using a phase difference birefringence measuring apparatus (KOBRA-WR, manufactured by Oji Scientific Instruments Co., Ltd.). The wavelength of the measurement light was 589 nm.

(Evaluation of glass transition temperature and linear expansion coefficient)

For the measurement of the glass transition temperature (referred to as Tg(1)) and the coefficient of linear expansion (CTE) in the room temperature region, the resin film having a sample length of 5 × 50 mm and a thickness of 20 μm which was cured at 350 ° C was manufactured by Shimadzu Corporation. Thermomechanical analysis device (TMA-50), according to thermomechanical analysis, measured the elongation of the test piece in the range of 5 g load, 10 ° C/min heating rate, nitrogen atmosphere (flow rate 20 ml/min), temperature 50-450 ° C, The bending point was determined as the glass transition temperature, and the CTE of the heat resistant resin film of 100 to 250 ° C was determined.

The glass transition temperature (referred to as Tg(2)) below the room temperature region cannot be measured by the above method. Therefore, the above-mentioned resin film is used in the range of -150 ° C to 400 ° C by a dynamic viscoelasticity measuring device (manufactured by Orientec, RHEOVIBRON MODEL). RHEO-1021) measurement The bending point in the temperature region below the room temperature of E-Prime is determined, and the bending point is determined as the glass transition temperature at a low temperature.

(Evaluation of residual stress)

Using a residual stress measuring device (manufactured by Tencor Corporation, model name FLX-2320), a resin composition was applied by a bar coater on a 6-inch wafer having a thickness of 625 μm ± 25 μm in which "warpage amount" was measured in advance. After prebaking at 140 ° C for 60 minutes, a vertical curing oven (manufactured by Koyo Lindberg Co., Ltd., model name VF-2000B) was used, and heat hardening treatment was performed at 350 ° C for 1 hour under a nitrogen atmosphere to prepare a hardened case. A germanium wafer of a resin film having a film thickness of 10 μm. The amount of warpage of the wafer was measured using the above-described residual stress measuring device, and the residual stress generated between the tantalum wafer and the resin film was evaluated.

(Evaluation of chemical resistance test)

The resin film having a thickness of 20 μm which was cured at 350 ° C was immersed in a NMP layer at room temperature, lifted every 10 minutes, washed with ion-exchanged water, and the surface of the film was observed by a microscope, and thermally hardened in 10 minutes. The time at which cracks occurred on the surface of the film was evaluated up to 300 minutes.

[Example 1]

Into a 3 L separable flask equipped with an oil bath with a stirring bar, 1000 g of NMP was added while introducing nitrogen gas, and 3,3-(diaminodiphenyl)anthracene (defined as diamine 1) was added while stirring. g, then 218.12 g of pyromellitic dianhydride (defined as tetracarboxylic anhydride 1) was added, and the mixture was stirred at room temperature for 30 minutes. The temperature was raised to 50 ° C, and after stirring for 12 hours, the amine-modified methylphenyl sulfonium oil (manufactured by Shin-Etsu Chemical Co., Ltd.: X22-1660B-3 (number average molecular weight 4400)) was prepared (defined as a thiol-containing diamine). 105.6 g was dissolved in 298 g of NMP, and added dropwise using a dropping funnel. The temperature was raised to 80 ° C, and after stirring for 1 hour, the oil bath was removed and the room temperature was returned to obtain a transparent polyacrylic acid NMP solution (hereinafter also referred to as varnish). The composition here and the weight average molecular weight (Mw) of the obtained polyamic acid are shown in Table 1. Further, the test results of the film cured at 350 ° C are shown in Table 4.

[Examples 2 to 33, 49 to 58]

In the same manner as in Example 1, the kinds of the diamine 1, the tetracarboxylic anhydride 1, the diamine-containing diamine, and the like were changed to those shown in Table 1, and the same as in Example 1 was carried out. Obtain varnish by operation. Further, the amount of NMP added shown in Tables 1 and 2 indicates the total amount of NMP contained in the final varnish, and includes the mass of 298 g of NMP diluted with a mercapto-containing diamine. The composition here and the weight average molecular weight (Mw) of the obtained polyamic acid are shown in Table 1, Table 2, and Table 7, respectively. Further, the test results of the film cured at 350 ° C are shown in Table 4, Table 5, and Table 8, respectively. Hereinafter, the names of the official compounds of the compound names shown in Tables 1 to 6 are indicated.

3,3-DAS: 3,3-(diaminodiphenyl)anthracene

4,4-DAS: 4,4-(diaminodiphenyl)anthracene

3,4-DAS: 3,4-(diaminodiphenyl)anthracene

PMDA: pyromellitic dianhydride

ODPA: 4,4'-oxydiphthalic dianhydride

6FDA: 4,4'-(hexafluoroisopropylidene)diphthalic anhydride

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

CHDA: cyclohexane-1,2,4,5-tetracarboxylic dianhydride

DSDA: 3,3',4,4'-diphenylphosphonium tetracarboxylic dianhydride

BPADA: 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride

BPAF: 9,9'-bis(3,4-dicarboxyphenyl)ruthenic anhydride

TAHQ: 4,4'-biphenyl bis(trimellitic acid monoester anhydride)

BTDA: 3,3',4,4'-benzophenone tetracarboxylic dianhydride

TPE-R: 1,3-bis(4-aminophenoxy)benzene

CBDA: 1,2,3,4-cyclobutane tetracarboxylic dianhydride

FM3311: Two-terminal amine-modified dimethyl hydrazine oil (Silaso FM3311 (quantitative average molecular weight 1000) manufactured by Chisso)

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

TACl: trimellitic anhydride chloride

[Example 34]

Nitrogen was introduced into a 3 L separable flask equipped with an oil bath with a stirring bar, and NMP 1274 g was added thereto, and 4,4'-oxydiphthalic dianhydride (hereinafter referred to as ODPA) (defined as tetracarboxylic anhydride) was added. 1), while stirring, a two-terminal amine-modified methylphenyl sulfonium oil (manufactured by Shin-Etsu Chemical Co., Ltd.: X22-1660B-3 (quantitative average molecular weight: 4,400)) was added by using a dropping funnel (specified as a thiol-containing diamine) 105.6g is dissolved in NMP 298g. After stirring at room temperature for 1 hour, 149.9 g of 2,2'-bis(trifluoromethyl)benzidine (hereinafter referred to as TFMB) (predetermined as diamine 2) was added while stirring, and then 3 was added while stirring. 3-DAS 116.2 g, stirred at room temperature for 1 hour. Subsequently, the mixture was heated to 50 ° C, and 147.1 g of BPDA (defined as tetracarboxylic anhydride 2) was added and stirred for 12 hours. The temperature was raised to 80 ° C, and after stirring for 4 hours, the oil bath was removed and the room temperature was returned to obtain a transparent polyacrylic acid NMP solution (hereinafter also referred to as varnish). The composition here and the weight average molecular weight (Mw) of the obtained polyamic acid are shown in Table 2. Further, the test results of the film cured at 350 ° C are shown in Table 5.

[Examples 35, 39, 40, 44, 45]

In the same manner as in Example 34, the kinds of the diamine 1, the diamine 2, the tetracarboxylic anhydride 1, the tetracarboxylic anhydride 2, and the like were changed to those shown in Table 2, respectively, and carried out in the same manner as in Example 34. The varnish was obtained in the same operation. Further, the amount of NMP added shown in Table 2 represents the total amount of NMP contained in the final varnish, and is a mass of 298 g of NMP diluted with a mercapto-containing diamine. The composition here and the weight average molecular weight (Mw) of the obtained polyamic acid are shown in Table 2, respectively. Further, the test results of the film cured at 350 ° C are shown in Table 5, respectively.

[Example 36]

Introduced in a 3L separable flask equipped with an oil bath with a stir bar 1196 g of N-methylpyrrolidone (hereinafter referred to as NMP) was added thereto, and 232.4 g of 3,3-(diaminodiphenyl)fluorene (predetermined as diamine 1) was added while stirring, and the temperature was raised to 50. After ° C, 147.1 g of BPDA (specified as tetracarboxylic anhydride 1) was added and stirred for 30 minutes. Next, 155.1 g of ODPA (defined as tetracarboxylic anhydride 2) was added and stirred for 8 hours, and then both ends of the amine-modified methylphenyl sulfonium oil (manufactured by Shin-Etsu Chemical Co., Ltd.: X22-1660B-3 (number average molecular weight 4400)) ( 105.6 g of a diamine containing a mercapto group was dissolved in NMP 298 g, and added dropwise using a dropping funnel. The temperature was raised to 80 ° C, and after stirring for 1 hour, the oil bath was removed and the room temperature was returned to obtain a transparent polyacrylic acid NMP solution (hereinafter also referred to as varnish). The composition here and the weight average molecular weight (Mw) of the obtained polyamic acid are shown in Table 2. Further, the test results of the film cured at 350 ° C are shown in Table 5.

[Examples 37, 42, 43, 46, 47]

In the same manner as in Example 36, the kinds of the diamine 1, the tetracarboxylic anhydride 1, the tetracarboxylic anhydride 2, and the like were changed to those shown in Table 2, and the same operation as in Example 36 was carried out. Get varnish. Further, the amount of NMP added shown in Table 2 represents the total amount of NMP contained in the final varnish, and is a mass of 298 g of NMP diluted with a mercapto-containing diamine. The composition here and the weight average molecular weight (Mw) of the obtained polyamic acid are shown in Table 2, respectively. Further, the test results of the film cured at 350 ° C are shown in Table 5, respectively.

[Example 38]

Into a 3 L separable flask equipped with an oil bath with a stirring bar, 1200 g of NMP was added while introducing nitrogen gas, and 3,3-(diaminodiphenyl)phosphonium (defined as diamine 1) was added while stirring. g. After heating to 50 ° C, 40.6 g of p-xylylene chloride (predetermined as a monomer component) was dissolved in 200 g of γ-butyrolactone, and the mixture was added dropwise and stirred for 30 minutes. Next, 235.4 g of BPDA (specified as tetracarboxylic anhydride 1) was added and stirred for 8 hours, and then both ends of the amine-modified methylphenyl sulfonium oil (manufactured by Shin-Etsu Chemical Co., Ltd.: X22-1660B-3 (number average molecular weight: 4,400)) ( 105.6 g of a diamine containing a mercapto group was dissolved in NMP 298 g, and added dropwise using a dropping funnel. Warm up to 80 ° C, stir for 1 hour, remove the oil bath While returning to room temperature, a solution of transparent polylysine was obtained. After 1000 g of NMP was added and diluted, the powder of the polyamidoximine precursor was precipitated while dropping 10 L of ion-exchanged water, and the powder was separated by filtration using a Buchner funnel. The powder was vacuum dried at 40 ° C for 48 hours. To the powder thus obtained, 1403 g of NMP was added to obtain a NMP solution of a polyamidoximine precursor. The composition here and the weight average molecular weight (Mw) of the obtained polyamidoximine precursor are shown in Table 2. Further, the test results of the film cured at 350 ° C are shown in Table 5.

[Examples 43, 48]

In the same manner as in Example 38, the kinds of the diamine 1, the tetracarboxylic anhydride 1, the other monomer components, and the like were changed to those shown in Table 2, and the same operation as in Example 38 was carried out. Get varnish. Further, the amount of NMP added shown in Table 2 indicates the total amount of NMP contained in the final varnish. The composition here and the weight average molecular weight (Mw) of the obtained polyamidoximine precursor are shown in Table 2, respectively. Further, the test results of the film cured at 350 ° C are shown in Table 5, respectively.

[Example 59]

In a 3 L separable flask equipped with an oil bath with a stirring bar, 1000 g of NMP was added while introducing nitrogen gas, and 3,3-(diaminodiphenyl)fluorene (defined as diamine 1) was added while stirring. g, followed by the addition of 275.13 g of BPDA (specified as tetracarboxylic anhydride 1), and the mixture was stirred at room temperature for 30 minutes. The temperature was raised to 50 ° C, and after stirring for 12 hours, 104.58 g of the acid anhydride-modified methylphenyl sulfonate (manufactured by Shin-Etsu Chemical Co., Ltd.: X22-168-P5-B (number average molecular weight 4200)) was dissolved in NMP 298 g. Add using a dropping funnel. The temperature was raised to 80 ° C, and after stirring for 1 hour, the oil bath was removed and the room temperature was returned to obtain a transparent polyacrylic acid NMP solution (hereinafter also referred to as varnish). The composition here and the weight average molecular weight (Mw) of the obtained polyamic acid are shown in Table 7. Further, the test results of the film cured at 350 ° C are shown in Table 8.

[Examples 60 to 66]

In the same manner as in Example 59, the kinds of the diamine 1, the tetracarboxylic anhydride 1, the diamine-containing diamine, and the like were changed to those shown in Table 1, and the same as in Example 1 was carried out. Obtain varnish by operation. Further, the amount of NMP added shown in Tables 1 and 2 indicates the total amount of NMP contained in the final varnish, and includes the mass of 298 g of NMP diluted with a mercapto-containing diamine. The composition here and the weight average molecular weight (Mw) of the obtained polyamic acid are shown in Table 7, respectively. Further, the test results of the film cured at 350 ° C are shown in Table 8, respectively.

[Comparative Example 1]

Into a 3 L separable flask equipped with an oil bath with a stirring bar, NMP 1065 g was added while introducing nitrogen gas, and 3,3-(diaminodiphenyl)phosphonium (defined as diamine 1) was added while stirring. g, then 218.12 g of pyromellitic dianhydride (defined as tetracarboxylic anhydride 1) was added, and the mixture was stirred at room temperature for 30 minutes. The temperature was raised to 50 ° C, and after stirring for 12 hours, the oil bath was removed and the room temperature was returned to obtain a transparent polyacrylic acid NMP solution (hereinafter also referred to as varnish). The composition here and the weight average molecular weight (Mw) of the obtained polyamic acid are shown in Table 3. Further, the test results of the film cured at 350 ° C are shown in Table 6.

[Comparative Example 2~21]

In the same manner as in Comparative Example 1, the types of the diamine 1, the tetracarboxylic anhydride 1, and the like were changed to those shown in Table 3, and the same operation as in Comparative Example 1 was carried out to obtain a varnish. The composition here and the weight average molecular weight (Mw) of the obtained polyamic acid are shown in Table 3, respectively. Further, the test results of the film cured at 350 ° C are shown in Table 6, respectively.

[Comparative Example 22]

In a 3 L separable flask equipped with an oil bath, a nitrogen gas was introduced, and NMP (133 g) was added thereto, and 299.8 g of TFMB (predetermined as diamine 2) was added while stirring, and 294.2 g of BPDA was added (specified as tetracarboxylic anhydride 1). ), warmed to 50 ° C, and stirred for 12 hours. Here, the two-terminal amine-modified methylphenyl eucalyptus oil was dropped using a dropping funnel (Shin-Etsu Chemical Co., Ltd. Production: X22-1660B-3 (number average molecular weight: 4,400)) (defined as a mercapto-containing diamine) 105.6 g was dissolved in NMP 298 g. After the completion of the dropwise addition, the temperature was raised to 80 ° C, and after stirring for 1 hour, the oil bath was removed and the room temperature was returned to obtain a somewhat turbid opaque polyacrylic acid NMP solution (hereinafter also referred to as varnish). The composition here and the weight average molecular weight (Mw) of the obtained polyamic acid are shown in Table 3. Further, the test results of the film cured at 350 ° C are shown in Table 6.

[Example 23]

Disperse 4.63 g (0.02 mol) of pyromellitic anhydride (PMDA) and 25.78 g of BTDA into 240 g of N-methyl-2-pyrrolidone (NMP), and titrate into ω-ω'-double-( 4-Aminopropyl)polydimethyloxane (average molecular weight: 480) 2.4 g of a solution obtained by dissolving in 50 g of diethylene glycol dimethyl ether (Dig), and stirring was carried out for 1 hour. Thus, after reacting the diamine sulfoxane with the tetracarboxylic dianhydride, 1,3-bis(4-aminophenoxy)benzene (TPE-R) 14.62 g (0.05 mol) was added in a powder amount. Ears, and then 3,3-DAS 11.17 g was added in portions with powder.

[Example 24]

A 1 liter flask equipped with a stirring device, a dropping funnel, a thermometer, a condenser, and a nitrogen substitution device was fixed in cold water. After substituting with nitrogen in the flask, 500 g of the N-methyl-2-pyrrolidone (hereinafter abbreviated as NMP) purified by dehydration, 3,3',4,4'-benzophenonetetracarboxylic dianhydride (BTDA) 25.11g (0.0779 mol), 3,3'-diaminodiphenylphosphonium (3,3-DAS) 15.48g (0.0623 mol) and ω-ω'-bis-(3- 14.96 g (0.0159 mol) of aminopropyl)polydimethyloxane (molecular weight 960) was mixed, and a polyaminic acid solution was obtained according to a usual method.

[Example 25]

In a 300 mL four-necked flask equipped with a thermometer, a stirrer, a nitrogen introduction tube, and a cooling tube, 2.87 g (25.1 mmol) of 1,4-diaminocyclohexane was added as a diamine compound, and the amine group was modified at both ends. Methylphenyl polyfluorene (X22-1660B-3) 3.42 g (0.8 mmol). Connect After replacing the inside of the flask with nitrogen, 58 ml of N,N-dimethylacetamide was added and stirred until uniform. To the obtained solution, as a polycarboxylic acid derivative, 8.71 g (25.9 mmol) of diphenyl-3,3',4,4'-tetracarboxylic dianhydride (BPDA) was added at room temperature, and Stirring was continued for 24 hours at this temperature to obtain a composition (polyglycine solution).

[Example 26]

4,4'-diamino-2,2'-bis(trifluoromethyl) linkage was added as a component (B) in a 300 mL four-necked flask equipped with a thermometer, a stirrer, a nitrogen introduction tube, and a cooling tube. Benzene (hereinafter, also referred to as "TFMB") 7.85 g (24.5 mmol) and 2.03 g (1.6 mmol) of a two-terminal amine-modified methylphenyl polyfluorene (X22-9409). Next, after nitrogen substitution in the flask, 58 ml of N,N-dimethylacetamide was added and stirred until uniform. To the obtained solution, as a component (A), 1,2,3,4-cyclobutanetetracarboxylic dianhydride (hereinafter also referred to as "CBDA") 5.12 g (26.1 mmol) was added at room temperature. And stirring was continued at this temperature for 24 hours to obtain a composition (polyglycine solution).

Further, the YI values and the total light transmittances shown in Tables 4 to 6 and Table 8 indicate the results (50 ppm/100 ppm/500 ppm) when the oxygen concentration in the oven was adjusted to 50 ppm, 100 ppm, and 500 ppm, respectively.

As shown in Tables 4, 5, and 8, it was confirmed that the physical properties of the films of Examples 1 to 66 satisfy the following conditions.

(1) Residual stress is 25 MPa or less

(2) The yellowness is below 7, and the effect of oxygen concentration is less

(3) The glass transition temperature in the temperature region above the room temperature is 250 ° C or higher

(4) The total light transmittance is above 88%, and the effect of oxygen concentration is less

(5) Tensile elongation of 30% or more

(6) NMP chemical resistance test for more than 30 minutes

(7) Even if a varnish is produced by NMP alone, the thermosetting film does not become cloudy, so the total light transmittance is high.

These satisfy the performance of the transparent substrate for a flexible display for use in a top emission type.

Examples 1 to 33, 36, 37, 41, 42, 46, 47, and 53 to 66 are derived from the film thickness direction of the birefringence, and the retardation Rth is 100 nm or less (20 to 90 nm), which is not only suitable for application to the top emission. The performance of the transparent substrate for a flexible display and the performance of the transparent substrate for a flexible display for a bottom emission type or an electrode substrate for a touch panel. Further, in the case of the retardation Rth in the thickness direction, a polyimide which does not use a monomer having a mercapto group as a copolymerization monomer (Comparative Examples 1 to 22) and a monomer which uses a mercapto group are used as a copolymerization sheet. Comparing the polyimines of the bodies (Examples 1 to 33), it is known that the polytheneimine of the monomer containing a mercapto group has a smaller Rth, and the monomer having a mercapto group is more conducive to the polyimine. Rth drops.

On the other hand, in Comparative Examples 1 to 26, residual stress, chemical resistance, and tensile elongation were low, and the YI value or total light transmittance was deteriorated by the influence of the oxygen concentration at the time of curing.

According to the results, it was confirmed that the resin obtained from the resin precursor of the present invention is colorless and transparent, and the residual stress generated between the inorganic film and the inorganic film is low, and further excellent in chemical resistance, and YI due to oxygen concentration at the time of curing. A resin film having a small influence on the value or total light transmittance.

Furthermore, the present invention is not limited to the above embodiment, and various modifications can be made.

[Industry use possibility]

The invention can be preferably used for manufacturing a semiconductor insulating film, a TFT-LCD insulating film, an electrode protective film, a flexible display, and can be preferably used as a substrate for a touch panel ITO electrode, and particularly preferably used. As a substrate.

Claims (27)

A resin precursor obtained by polymerizing a polymerization component containing an amine group and an amine group reactive group, and the polymerization component contains a polyvalent compound having two or more groups selected from an amine group and an amine group reactive group The above polyvalent compound comprises a thiol group-containing compound, and the above polyvalent compound comprises a diamine represented by the following formula (1): The above resin precursor has a structure represented by the following formula (2): In the formula, R ₃ and R ₄ are each independently a one-carbon organic group having 1 to 20 carbon atoms, and h is an integer of 3 to 200. The amount of the above-mentioned compound containing a mercapto group is the above-mentioned polyvalent compound. The total mass basis is 6 mass% to 25% by mass, and the diamine represented by the above formula (1) accounts for 50 mol% or more of all diamines. The resin precursor of claim 1, wherein the above amine reactive group is selected from the group consisting of carboxylic acid One or more selected from the group consisting of a substituted carboxyl group and an acid anhydride group. The resin precursor according to claim 1 or 2, wherein the thiol group-containing compound comprises a polyoxonium compound represented by the following formula (3): In the formula, a plurality of R ₂ are independently a single bond or a divalent organic group having 1 to 20 carbon atoms, and R ₃ and R ₄ are each independently a one-carbon organic group having 1 to 20 carbon atoms, and a plurality of organic groups may exist. R _{5 is} independently a monovalent organic group having 1 to 20 carbon atoms, and L ₁ , L ₂ and L ₃ are each independently an amine group, an isocyanate group, a carboxyl group, an acid anhydride group, an acid ester group, a fluorenyl group, a hydroxyl group, and a ring. An oxy or fluorenyl group, j is an integer from 3 to 200, and k is an integer from 0 to 197}. The resin precursor of claim 3, wherein, in the above formula (3), L ₁ and L ₂ are each independently an amine group or an acid anhydride group, and k is 0. The resin precursor of claim 4, wherein, in the above formula (3), both of L ₁ and L ₂ are an amine group. The resin precursor according to claim 1 or 2, wherein the resin precursor contains the unit 1 and the unit 2, and the unit 1 has at least the structure represented by the following formula (4): In the formula, there are a plurality of R ₁ independently being a hydrogen atom, a carbon number of 1 to 20, a monovalent aliphatic hydrocarbon group or a monovalent aromatic group, and there may be a plurality of X ₁ independently of carbon numbers 4 to 32. a tetravalent organic group, and n is an integer of from 1 to 100}, and the unit 2 has a structure represented by the following formula (5): In the formula, a plurality of R ₁ are independently a hydrogen atom, a carbon number of 1 to 20, a monovalent aliphatic hydrocarbon group or a monovalent aromatic group, and a plurality of R ₂ are independently 3 to 20 carbon atoms. a valence aliphatic hydrocarbon group or a divalent aromatic group, R ₃ and R ₄ are each independently a one-carbon organic group having 1 to 20 carbon atoms, and a plurality of X ₂ organic groups independently having a carbon number of 4 to 32 may be present. , l is an integer from 3 to 50, and m is an integer from 1 to 100}, or a structure represented by the following formula (6): In the formula, there are a plurality of R ₁ independently being a hydrogen atom, a carbon number of 1 to 20, a monovalent aliphatic hydrocarbon group or a monovalent aromatic group, and a plurality of R ₃ and R ₄ are independently a carbon number 1~ 20 one-valent organic group, a plurality of R ₈ are independently a trivalent aliphatic hydrocarbon group or a trivalent aromatic group having 3 to 20 carbon atoms, p is an integer of 1 to 100, and q is an integer of 3 to 50 } or both the structure represented by the above formula (5) and the structure represented by the above formula (6). The resin precursor of claim 6, wherein the total amount of the unit 1 and the unit 2 is 30% by mass or more based on the total mass of the resin precursor. The resin precursor of claim 6, wherein the resin precursor further contains a unit 3 having a structure represented by the following formula (7): In the formula, a plurality of R ₁ are independently a hydrogen atom, a carbon number of 1 to 20, a monovalent aliphatic hydrocarbon group or a monovalent aromatic group, and a plurality of X ₃ may be independently a carbon number of 4 to 32. The divalent organic group may have a plurality of X ₄ independently independently a tetravalent organic group having a carbon number of 4 to 32, and t is an integer of 1 to 100}. The resin precursor of claim 8, wherein in the above formula (7), X ₃ is a residue of a structure obtained by removing an amine group from 2,2'-bis(trifluoromethyl)benzidine. The resin precursor according to claim 6, wherein the unit 1 and the unit 2 are contained in an amount of 60 mol% or more based on the total amount of the acid dianhydride-derived portion of the unit 1 and the unit 2, as follows A portion of the combination of the two parts, which is derived from a part or a source selected from the group consisting of pyromellitic dianhydride (PMDA) and biphenyltetracarboxylic dianhydride (BPDA) Self-selected from 4,4'-oxydiphthalic dianhydride (ODPA), 4,4'-(hexafluoroisophthalene) Propyl)diphthalic anhydride (6FDA), cyclohexane-1,2,4,5-tetracarboxylic dianhydride (CHDA), 3,3',4,4'-diphenylphosphonium tetracarboxylate Acid dianhydride (DSDA), 4,4'-biphenyl bis(trimellitic acid monoester anhydride) (TAHQ) and 9,9'-bis(3,4-dicarboxyphenyl)ruthenic anhydride (BPAF) One or more parts of the group formed. The resin precursor according to claim 1 or 2, wherein the R ₃ and the R ₄ are each independently a monovalent aliphatic hydrocarbon group having 1 to 3 carbon atoms or a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms. The resin precursor according to claim 1 or 2, wherein at least a part of the above R ₃ and the above R ₄ is a phenyl group. The resin precursor according to claim 1 or 2, wherein the resin obtained by heat-hardening the resin precursor under an inert gas atmosphere at 300 to 500 ° C has at least 1 in a region of -150 ° C to 0 ° C. The glass transition temperature and at least one glass transition temperature in a region of 150 ° C to 380 ° C, and no glass transition temperature in a region greater than 0 ° C and less than 150 ° C. The resin precursor according to claim 1 or 2, which comprises from biphenyltetracarboxylic dianhydride (BPDA) in an amount of 20 mol% or more based on the total amount of the acid dianhydride-derived portion of the above-mentioned resin precursor. The part. A resin precursor of claim 1 or 2, a portion of which is imidized by hydrazine. A precursor mixture comprising the resin precursor according to any one of claims 1 to 15 and a resin precursor having a structure represented by the following formula (8): In the formula, a plurality of X ₃ may be independently a tetravalent organic group having a carbon number of 4 to 32, and a plurality of R ₁ are independently a hydrogen atom, a carbon number of 1 to 20, a monovalent aliphatic hydrocarbon group or a Avalent aromatic group, and r is an integer from 1 to 100}. A flexible device material comprising the resin precursor of any one of claims 1 to 15 or a precursor mixture of claim 16. A resin film which is a cured product of the resin precursor of any one of claims 1 to 15 or a cured product of the precursor mixture of claim 16. A resin composition comprising the resin precursor according to any one of claims 1 to 15 or a precursor mixture and a solvent as claimed in claim 16. The resin composition of claim 19, wherein after the resin composition is developed on the surface of the support, the resin composition is heated by heating the resin composition at 300 ° C to 500 ° C under a nitrogen atmosphere. The resin obtained by the ruthenium imidization of the resin precursor contained in the resin has a yellowness of 7 or less when the film thickness is 20 μm. The resin composition of claim 19 or 20, wherein after the resin composition is spread on the surface of the support, the resin is heated by heating at 300 ° C to 500 ° C under a nitrogen atmosphere. The resin obtained by the ruthenium iodization of the resin precursor contained in the composition has a residual stress of 25 MPa or less when the film thickness is 10 μm. A resin film which is a cured product of the resin composition according to any one of claims 19 to 21. A method of producing a resin film, comprising the steps of: developing a resin composition according to any one of claims 19 to 21 on a surface of a support; and heating the support and the resin composition to cause the resin The resin precursor contained in the composition is imidized to form a resin film, and the resin film is peeled off from the support. A laminate comprising a support and a resin film of a cured product of the resin composition according to any one of claims 19 to 21 formed on the surface of the support. A method for producing a laminate comprising the steps of: developing a resin composition according to any one of claims 19 to 21 on a surface of a support; and heating the support and the resin composition to cause the resin The resin precursor contained in the composition is imidized to form a resin film, thereby obtaining a laminate including the support and the resin film. A polyimide film which is a user of a display substrate and has an Rth of 20 to 90 nm when the thickness is 20 μm. A method for manufacturing a display substrate, comprising the steps of: developing a resin composition containing a polyimide precursor on a surface of a support; and heating the support and the resin composition to form a polyimide precursor Performing hydrazine imidization to form a polyimine resin film according to claim 26; forming an element on the above polyimide film; and forming the above-mentioned polyimine resin film having the above element from the support Stripped.