KR20200103734A - Hybrid resin composition - Google Patents

Abstract

[Task] A flexible display substrate that can be easily peeled from a supporting substrate or a peeling layer formed thereon while maintaining excellent performance of excellent heat resistance, low retardation, excellent flexibility, and excellent transparency. It is an object of the present invention to provide a resin composition that imparts a plastic thin film having excellent performance as a base film for a flexible device substrate such as.
[Solution means] An organic-inorganic hybrid resin composition comprising the following (A) component, (B) component and (C) component. (A) component: inorganic fine particles having an average particle diameter of 1 nm to 100 nm, modified on the surface of the fine particles with an alkoxysilane compound having two aromatic groups having 6 to 18 carbon atoms or one aromatic group having 7 to 18 carbon atoms, (B ) Component: fluorine-containing polyimide, (C) component: organic solvent.

Description

Hybrid resin composition

The present invention relates to a hybrid resin composition, and more particularly, particularly, of a flexible device substrate such as a flexible display, capable of forming a film capable of being peeled off by a mechanical peeling method from a peeling layer formed on a carrier substrate. It relates to a composition that can be used suitably for formation.

In recent years, with rapid advances in electronics such as liquid crystal displays and organic electroluminescent displays, thinner, lighter, and more flexible devices have been demanded.

In these devices, various electronic devices, such as thin film transistors and transparent electrodes, are formed on a glass substrate. By replacing this glass material with a flexible and lightweight resin material, the device itself is thinner or lighter. It is expected to promote flexibility.

As a candidate for such a resin material, polyimide has attracted attention, and various reports have been made regarding polyimide films.

For example, Patent Document 1 relates to a polyimide useful as a plastic substrate for a flexible display, and an invention related to its precursor, and includes tetracarboxylic acids including alicyclic structures such as cyclohexylphenyltetracarboxylic acid, and various diamines. It is reported that the reacted polyimide is excellent in transparency and heat resistance.

In addition, in Patent Document 2, by adding silica sol to polyimide, both the linear expansion coefficient, transparency, and low birefringence, which were the drawbacks of conventional plastic substrates, are improved, and application to plastic substrates for flexible displays can be sufficiently expected. have.

On the other hand, when the advantage of the plastic substrate is added, a problem is the handleability and dimensional stability of the plastic substrate itself. In other words, if the plastic substrate is made thin, wrinkles and cracks are likely to occur, making it difficult to ensure self-support, and also, positioning accuracy when layering functional layers such as thin film transistors (TFTs) and electrodes. B. It becomes difficult to maintain the dimensional accuracy after forming the functional layer. Accordingly, in Non-Patent Document 1, a method of forcibly separating the plastic substrate with the functional layer from the glass by forming a predetermined functional layer on a plastic substrate coated and fixed on glass, and then irradiating a laser from the glass side. (A so-called laser lift-off process (a method called EPLaR (Electronics on Plastic by Laser Release)) has been proposed.

Japanese Patent Publication No. 2008-231327 International Publication No. 2015/152178

E.I. Haskal et. al. “Flexible OLED Displays Made with the EPLaR Process”, Proc. Eurodisplay ’07,pp.36-39 (2007)

The technique described in the above-described Non-Patent Document 1 uses glass as a supporting substrate and forms a functional layer on a plastic substrate fixed to the glass, thereby ensuring the handling properties and dimensional stability of the resin substrate. However, this EPLaR method (laser lift-off method) is a method of destroying the interface between the resin substrate and the support substrate by laser irradiation when separating the resin substrate from the support substrate. Therefore, the functional layer (TFT Etc.) is damaged, the resin substrate itself is greatly damaged, so that the transmittance is lowered, there is a concern of deteriorating the properties of the resin substrate and the functional layer formed thereon.

The present invention has been made in view of these circumstances, and provides a resin composition that imparts a plastic thin film having excellent performance as a base film for a flexible device substrate such as a flexible display substrate, which does not conform to the above laser lift-off technology, In particular, it maintains excellent performance of excellent heat resistance, low retardation, excellent flexibility, and excellent transparency, while ensuring its handling and dimensional stability, and mechanical peeling. An object of the present invention is to provide a resin composition for providing a substrate for a flexible device capable of being peeled from a support substrate or a release layer, and a substrate for a flexible device obtained therefrom.

The present inventors, as a result of repeated scrutiny in order to achieve the above object, showed that a resin composition in which silica sol modified with a specific siloxane was blended with a heat-resistant polymer adopted to achieve both heat resistance and optical properties has excellent heat resistance. And, while maintaining the characteristics of low retardation, excellent flexibility, and excellent transparency, it was found that it was possible to form a thin film easily peeled from a support substrate, etc., and the present invention was completed.

That is, as a first aspect, the present invention relates to an organic-inorganic hybrid resin composition comprising the following (A) component, (B) component and (C) component.

(A) component: inorganic fine particles having an average particle diameter of 1 nm to 100 nm, modified with an alkoxysilane compound having two aromatic groups having 6 to 18 carbon atoms or one aromatic group having 7 to 18 carbon atoms,

(B) component: polyimide having fluorine,

(C) Component: Organic solvent.

As a second aspect, it relates to the organic-inorganic hybrid resin composition according to the first aspect, wherein the alkoxysilane compound in the component (A) is a compound represented by the following formula (S1).

[Formula 1]

(In the formula,

R ¹ and R ² are each independently an alkyl group having 1 to 3 carbon atoms,

W is an integer from 1 to 3,

Y is an integer of 0-2, and W+Y=3,

Z ¹ represents a group selected from the group consisting of a halogen atom, an alkyl group having 1 to 10 carbon atoms, and an alkoxy group having 1 to 10 carbon atoms, m represents an integer of 0 to 5, provided that when m is an integer of 2 or more, Z ¹ May be the same or different groups.)

As a third aspect, it relates to the organic-inorganic hybrid resin composition according to the first aspect or the second aspect, wherein m is 0 in the above formula.

As a fourth aspect, the polyimide of the component (B) is an imide of polyamic acid, which is a reaction product of a tetracarboxylic acid dianhydride component and a diamine component containing a fluorinated aromatic diamine represented by the following formula (A1). It relates to the organic-inorganic hybrid resin composition according to any one of the first to third viewpoints, which is a cargo.

[Formula 2]

(In the formula, B ² represents a divalent group selected from the group consisting of formulas (Y-1) to (Y-34).)

[Formula 3]

[Formula 4]

[Formula 5]

[Formula 6]

[Formula 7]

(In the formula, * represents the number of bonds.)

As a fifth aspect, it relates to the organic-inorganic hybrid resin composition according to the fourth aspect, wherein the tetracarboxylic acid dianhydride component contains an alicyclic tetracarboxylic acid dianhydride represented by the following formula (C1).

[Formula 8]

[In the formula, B ¹ represents a tetravalent group selected from the group consisting of formulas (X-1) to (X-12).

[Formula 9]

(In the formula, a plurality of R represents a hydrogen atom or a methyl group independently of each other, and * represents the number of bonds.)

As a sixth viewpoint, it relates to the organic-inorganic hybrid resin composition according to any one of the first to fifth viewpoints, wherein the inorganic fine particles of the component (A) are silicon dioxide particles.

As a seventh viewpoint, the mass ratio of the component (A) and the component (B) is 5:5 to 9::1 in (A):(B), the organic-inorganic according to any one of the first to sixth viewpoints It relates to a hybrid resin composition.

As an eighth aspect, it relates to the organic-inorganic hybrid resin composition according to any one of the first to seventh aspects, wherein the inorganic fine particles of the component (A) are inorganic fine particles having an average particle diameter of 1 nm to 60 nm.

As a ninth aspect, it relates to the organic-inorganic hybrid resin composition according to any one of the first to eighth aspects, wherein the component (C) is an ester solvent.

As a tenth viewpoint, it relates to a resin thin film formed from the organic-inorganic hybrid resin composition according to any one of the first to ninth viewpoints, which is transparent with a light transmittance of 80% or more at 400 nm and has a haze of 2% or less. will be.

As an eleventh viewpoint, it is related with the board|substrate for flexible devices which consists of the resin thin film of 10th viewpoint.

As a twelfth aspect, as a method of manufacturing a substrate for a flexible device,

a) forming a release layer on the support substrate;

b) a step of forming a resin thin film to be a substrate for flexible devices comprising the organic-inorganic hybrid resin composition according to any one of the first to ninth viewpoints on this release layer; And

c) removing the resin thin film from the peeling layer to obtain a flexible device substrate;

It relates to a method, including.

According to the organic-inorganic hybrid resin composition according to one aspect of the present invention, it is possible to form a resin thin film having a low coefficient of linear expansion, excellent heat resistance, low retardation, and excellent flexibility, and furthermore, from a support substrate without impairing these performances. It is possible to form a resin thin film that is easily peeled.

And the resin thin film formed from the organic-inorganic hybrid resin composition of the present invention exhibits high heat resistance, low coefficient of linear expansion, high transparency (high light transmittance, low yellowness), low retardation, and is also excellent in flexibility. In particular, it can be suitably used as a base film for a flexible display substrate.

The organic-inorganic hybrid resin composition according to the present invention and the resin thin film formed therefrom are substrates for flexible devices that require properties such as high flexibility, low coefficient of linear expansion, high transparency (high light transmittance, low yellowness), and low retardation. In particular, it is capable of sufficiently responding to progress in the field of flexible display substrates.

Fig. 1 is a schematic diagram of a method of peeling a substrate for a flexible device obtained from the organic-inorganic hybrid resin composition of the present invention from a support substrate.

Hereinafter, the present invention will be described in detail.

The organic-inorganic hybrid resin composition of the present invention contains (A) component: inorganic fine particles modified with a specific alkoxysilane, (B) component: the following specific polyimide, and (C) component: an organic solvent. Therefore, it contains a crosslinking agent and other components.

[(A) Component: Inorganic fine particles whose surface is modified with specific alkoxysilane]

The component (A) is an inorganic fine particle obtained by modifying the surface of the fine particle with a specific alkoxysilane described later. These inorganic fine particles can appropriately select their average particle diameter depending on the purpose or the like. Among them, from the viewpoint of obtaining a more highly transparent thin film, the average particle diameter is preferably 1 nm to 100 nm, for example, 1 nm to 60 nm, or more preferably 9 nm to 60 nm, and particularly preferably 9 nm to 45 nm.

In the present invention, the average particle diameter of inorganic fine particles is an average particle diameter value calculated from a specific surface area value measured by a nitrogen adsorption method using inorganic fine particles.

As the inorganic fine particles, in particular, in the present invention, silica (silicon dioxide) particles, for example, colloidal silica having the value of the average particle diameter may be suitably used, and silica sol may be used as the colloidal silica. have. As the silica sol, an aqueous silica sol prepared by a known method using an aqueous sodium silicate solution as a raw material, and an organo silica sol obtained by substituting water as a dispersion medium of the aqueous silica sol with an organic solvent can be used.

In addition, silica obtained by hydrolyzing an alkoxysilane such as methyl silicate or ethyl silicate in the presence of a catalyst (e.g., ammonia, an organic amine compound, an alkali catalyst such as sodium hydroxide) in an organic solvent such as alcohol, and condensation. A sol or an organosilica sol obtained by solvent-replacement of the silica sol with another organic solvent may also be used.

Among these, in the present invention, it is preferable to use organosilica sol whose dispersion medium is an organic solvent.

Examples of the organic solvent in the organosilicarsol described above include lower alcohols such as methyl alcohol, ethyl alcohol and isopropanol; Linear amides such as N,N-dimethylformamide and N,N-dimethylacetamide; Cyclic amides such as N-methyl-2-pyrrolidone; ethers such as γ-butyrolactone; And glycols such as ethyl cellosolve and ethylene glycol, and acetonitrile.

Substitution of water, which is a dispersion medium of the aqueous silica sol, or substitution with another target organic solvent can be performed by a conventional method such as distillation method, ultrafiltration method, or the like.

The viscosity of the organosilicasol is about 0.6 mPa·s to 100 mPa·s at 20°C.

Examples of commercially available products of the organo silica sol include, for example, the brand name MA-ST-S (methanol-dispersed silica sol, Nissan Chemical Industries Co., Ltd. (now: Nissan Chemical Co., Ltd., hereinafter the same)), the brand name MT- ST (Methanol Dispersion Silicasol, Nissan Chemical Industries Co., Ltd.), brand name MA-ST-UP (Methanol Dispersion Silicasol, Nissan Chemical Industries Co., Ltd.), brand name MA-ST-M (Methanol Dispersion Silicasol, Nissan Chemical Industry Co., Ltd.), brand name MA-ST-L (methanol dispersion silica sol, Nissan Chemical Industry Co., Ltd. product), brand name IPA-ST-S (isopropanol dispersion silica sol, Nissan Chemical Industry Co., Ltd. product), Brand name IPA-ST (isopropanol-dispersed silica sol, manufactured by Nissan Chemical Industries, Ltd.), brand name IPA-ST-UP (isopropanol-dispersed silica sol, Nissan Chemical Industries Co., Ltd.), brand name IPA-ST-L (isopropanol-dispersed silica) Sol, Nissan Chemical Industries Co., Ltd., brand name IPA-ST-ZL (isopropanol-dispersed silica sol, Nissan Chemical Industries Co., Ltd.), brand name NPC-ST-30 (n-propyl cellosolve-dispersed silica sol, Nissan) Chemical Industry Co., Ltd.), brand name PGM-ST (1-methoxy-2-propanol-dispersed silica sol, Nissan Chemical Industry Co., Ltd. product), brand name DMAC-ST (dimethylacetamide-dispersed silica sol, Nissan Chemical Industry ( Co., Ltd.), brand name XBA-ST (xylene-n-butanol mixed solvent-dispersed silica sol, manufactured by Nissan Chemical Industries, Ltd.), brand name EAC-ST (ethyl acetate-dispersed silica sol, manufactured by Nissan Chemical Industries, Ltd.) , Brand name PMA-ST (propylene glycol monomethyl ether acetate-dispersed silica sol, manufactured by Nissan Chemical Industries, Ltd.), brand name MEK-ST (methyl ethyl ketone-dispersed silica sol, manufactured by Nissan Chemical Industries, Ltd.), brand name MEK-ST -UP (Methyl ethyl ketone-dispersed silica sol, manufactured by Nissan Chemical Industries, Ltd.), brand name MEK-ST-L (methyl ethyl ketone-dispersed silica sol, manufactured by Nissan Chemical Industries, Ltd.) and brand name MIBK-ST (methylisobutyl) Ketone-dispersed silica sol, Nissan Chemical Industry Co., Ltd., PL-1-IPA (isopropanol-dispersed silica sol, Fuso Chemical Industry Co., Ltd.), PL-1-TOL (toluene-dispersed silica sol, Fuso Chemical Co., Ltd.) ), PL-2L-PGME (Propylene glycol monomethyl ether-dispersed silica sol, Fuso Chemical Industries Co., Ltd.), PL-2L-MEK (methyl ethyl ketone-dispersed silica sol, Fuso Chemical Co., Ltd.) ), PL-3-ME (methanol-dispersed silica sol, manufactured by Fuso Chemical Industries, Ltd.), and the like, but are not limited to these.

In the present invention, silicon dioxide, for example, silicon dioxide as mentioned in the product used as organosilicarsol may be used in combination of two or more.

[Specific alkoxysilane]

In the present invention, the alkoxysilane compound (hereinafter referred to as a specific alkoxysilane) used for modifying inorganic fine particles is an alkoxysilane compound having two aromatic groups having 6 to 18 carbon atoms, or an aromatic group having 7 to 18 carbon atoms. It is an alkoxysilane compound having one.

Examples of the aromatic group having 6 to 18 carbon atoms include a phenyl group and an aromatic group having 7 to 18 carbon atoms described later. Examples of the aromatic group having 7 to 18 carbon atoms include a group having 2 to 3 benzene rings, and a group having 2 to 4 condensed benzene rings. Among them, an alkoxysilane having a biphenyl group as an aromatic group having 7 to 18 carbon atoms and having a structure represented by the following formula (S1) is preferable.

[Formula 10]

In the formula,

R ¹ and R ² are each independently an alkyl group having 1 to 3 carbon atoms,

W is an integer from 1 to 3,

Y is an integer of 0-2, and W+Y=3,

Z ¹ represents a group selected from the group consisting of a halogen atom, an alkyl group having 1 to 10 carbon atoms, and an alkoxy group having 1 to 10 carbon atoms, m represents an integer of 0 to 5, provided that when m is an integer of 2 or more, Z ¹ Can be the same or different groups.

Among them, an alkoxysilane in which m is 0 (the biphenyl group is not substituted) is preferable.

Examples of the alkoxysilane compound represented by the above formula (S1) include 4-biphenyltrimethoxysilane, 4-biphenyltriethoxysilane, 3-biphenyltrimethoxysilane, and 3-biphenyltriethoxysilane. And the like.

Inorganic fine particles having a surface modified with a specific alkoxysilane can be prepared, for example, by bringing a specific alkoxysilane into contact with silica particles when silica particles are used as inorganic fine particles. When a specific alkoxysilane and silica particles are brought into contact, for example, a silanol group or an alkoxysilyl group in a specific alkoxysilane is bonded by a condensation reaction with a hydroxyl group present on the surface of the silica particle, and the surface is modified with a specific alkoxysilane. Is thought to be formed.

Specifically, for example, by mixing a colloidal solution of silica particles and a specific alkoxysilane solution prepared in advance, silica particles having a surface modified with a specific alkoxysilane can be prepared. The colloidal solution and the specific alkoxysilane solution may be mixed at room temperature or while heating. From the viewpoint of reaction efficiency, it is preferable to perform mixing while heating. When mixing is carried out while heating, the heating temperature can be appropriately selected depending on the solvent or the like. The heating temperature can be, for example, 60°C or higher, and is preferably the reflux temperature of the solvent.

The mixing ratio of the specific alkoxysilane and silica particles can be appropriately selected depending on the purpose and the like. For example, the mass ratio (silica particle/specific alkoxysilane) of the silica particles to the specific alkoxysilane is preferably 70/30 to 99/1, more preferably 70/30 to 90/10, and 80/ It is more preferably 20 to 90/10. Here, as for the mass number of silica particles, the composition formula of the silica particles is calculated as SiO ₂ .

[(B) component: polyimide]

The polyimide suitably used in the present invention is a polyimide containing fluorine, and more specifically, a polyamic acid (reaction product) obtained by reacting a tetracarboxylic acid dianhydride component and a diamine component containing a fluorinated aromatic diamine. It is a polyimide (imide product) obtained by imidation.

Among them, it is preferable that the fluorinated aromatic diamine contains a diamine represented by the following formula (A1).

[Formula 11]

(In the formula, B ² represents a divalent group selected from the group consisting of formulas (Y-1) to (Y-34).)

[Formula 12]

[Formula 13]

[Formula 14]

[Formula 15]

[Formula 16]

(In the formula, * represents the number of bonds.)

As the tetracarboxylic dianhydride component, it is preferable to use an alicyclic tetracarboxylic dianhydride from the viewpoint of transparency and solubility in a solvent.

Among them, it is preferable that the alicyclic tetracarboxylic dianhydride contains a tetracarboxylic dianhydride represented by the following formula (C1).

[Formula 17]

[In the formula, B ¹ represents a tetravalent group selected from the group consisting of formulas (X-1) to (X-12).

[Formula 18]

(In the formula, a plurality of R represents a hydrogen atom or a methyl group independently of each other, and * represents the number of bonds.)

Among the tetracarboxylic dianhydride represented by the above formula (C1), B ¹ in the formula is a compound represented by formulas (X-1), (X-4), (X-6), and (X-7). desirable.

Further, among the diamines represented by the above (A1), it is preferable that B ² in the formula is a compound represented by the formulas (Y-12) and (Y-13).

As a suitable example, a polyimide obtained by imidizing a polyamic acid obtained by reacting a tetracarboxylic acid dianhydride represented by the formula (C1) with a diamine represented by the formula (A1) is represented by the formula (2) described later. Includes the displayed monomer unit.

In order to obtain a resin thin film (substrate for flexible devices) having low linear expansion coefficient, low retardation, and high transparency, which is an object of the present invention, and having excellent flexibility, alicyclic tetracarb is used in relation to the total number of moles of the tetracarboxylic dianhydride component. The main acid dianhydride, for example, the tetracarboxylic acid dianhydride represented by the above formula (C1) is preferably 90 mol% or more, more preferably 95 mol% or more, and particularly all (100 mol%) of the above formula (C1) It is optimal that it is tetracarboxylic dianhydride represented by ).

Similarly, in order to obtain a resin thin film (substrate for flexible devices) having the above low linear expansion coefficient, low retardation, and high transparency characteristics and excellent flexibility, based on the total number of moles of the diamine component, a fluorinated aromatic diamine, for example It is preferable that the diamine represented by formula (A1) is 90 mol% or more, and it is more preferable that it is 95 mol% or more. In addition, all (100 mol%) of the diamine component may be a diamine represented by the above formula (A1).

As an example of a suitable embodiment, the polyimide used in the present invention contains a monomer unit represented by the following formula (1).

[Formula 19]

As a monomer unit represented by the said formula (1), it is preferable that it is represented by a formula (1-1) or a formula (1-2), and it is more preferable that it is represented by a formula (1-1).

[Formula 20]

According to a preferred aspect of the present invention, the polyimide used in the present invention contains a monomer unit represented by formula (2). The polyimide used in the present invention may contain a monomer unit represented by formula (1) and a monomer unit represented by formula (2) at the same time.

[Formula 21]

As the monomer unit represented by the above formula (2), it is preferred to be represented by formula (2-1) or (2-2), and more preferably represented by formula (2-1).

[Formula 22]

When the polyimide used in the present invention contains a monomer unit represented by formula (1) and a monomer unit represented by formula (2), the molar ratio in the polyimide chain is a monomer unit represented by formula (1). : The monomer unit represented by formula (2) = 10: It is preferable to include in a ratio of 1 to 1: 10, More preferably, it is preferably included in a ratio of 8: 2 to 2: 8, and 6: 4 to It is more preferable to include it in a ratio of 4:6.

The polyimide of the present invention is derived from an alicyclic tetracarboxylic dianhydride component containing a tetracarboxylic dianhydride represented by the above formula (C1), and a diamine component containing a diamine represented by formula (A1). In addition to the monomer unit, for example, the monomer unit represented by the above formulas (1) and (2), other monomer units may be included. The content ratio of other monomer units is arbitrarily determined as long as the properties of the resin thin film formed from the organic-inorganic hybrid resin composition of the present invention are not impaired.

The ratio is a monomer unit derived from an alicyclic tetracarboxylic dianhydride component containing a tetracarboxylic acid dianhydride represented by the above formula (C1) and a diamine component containing a diamine represented by formula (A1), For example, with respect to the number of moles of the monomer unit represented by formula (1) or the monomer unit represented by formula (2), or the total number of moles of the monomer unit represented by formula (1) and the monomer unit represented by formula (2) On the other hand, less than 20 mol% is preferable, less than 10 mol% is more preferable, and it is still more preferable that it is less than 5 mol%.

Examples of such other monomer units include monomer units having different polyimide structures represented by formula (3), but are not limited thereto.

[Formula 23]

In formula (3), A represents a tetravalent organic group, and preferably represents a tetravalent group represented by any one of the following formulas (A-1) to (A-4). In addition, in the above formula (3), B represents a divalent organic group, and preferably represents a divalent group represented by any one of formulas (B-1) to (B-11). In each formula, * represents the number of bonds. On the other hand, in formula (3), when A represents a tetravalent group represented by any one of the following formulas (A-1) to (A-4), B is the aforementioned formulas (Y-1) to (Y-34) It may be a divalent group represented by either one. Alternatively, in formula (3), when B represents a divalent group represented by any one of the following formulas (B-1) to (B-11), A is in the above formulas (X-1) to (X-12) It may be a tetravalent group represented by any one.

When a monomer unit represented by formula (3) is included in the polyimide used in the present invention, A and B may contain only a monomer unit composed of only one of the groups exemplified in the following formula, for example, , At least one of A and B may contain two or more kinds of monomer units selected from two or more kinds of groups exemplified below.

[Formula 24]

[Formula 25]

On the other hand, in the polyimide used in the present invention, each monomer unit is bonded in an arbitrary order.

As a suitable example, the polyimide having a monomer unit represented by the above formula (1) is bicyclo[2,2,2]octane-2,3,5,6-tetracarboxylic acid as a tetracarboxylic dianhydride component. It is obtained by polymerizing a dianhydride and a diamine represented by the following formula (4) as a diamine component in an organic solvent to imidize the resulting polyamic acid.

In addition, when the polyimide used in the present invention has a monomer unit represented by the above formula (2), this polyimide contains 1,2,3,4-cyclobutanetetracarboxylic acid as a tetracarboxylic dianhydride component. It is obtained by polymerizing an anhydride and a diamine represented by the following formula (4) as a diamine component in an organic solvent to imidize the resulting polyamic acid.

Furthermore, when the polyimide used in the present invention has a monomer unit represented by the formula (2) in addition to the monomer unit represented by the formula (1), each of the formulas (1) and (2) In addition to the tetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride and the diamine component of the polyimide containing the monomer unit are represented by the following formula (4) It is obtained by making the displayed diamine polymerize in an organic solvent, and imidizing the obtained polyamic acid.

[Formula 26]

As the diamine represented by the above formula (4), 2,2'-bis(trifluoromethyl)benzidine, 3,3'-bis(trifluoromethyl)benzidine, 2,3'-bis(trifluoromethyl)benzidine, 2,3'-bis(trifluoromethyl)benzidine Methyl) benzidine.

Among them, as the diamine component, from the viewpoint of lowering the linear expansion coefficient of the resin thin film (substrate for flexible devices) of the present invention and higher transparency of the resin thin film (substrate for flexible devices), the following formula (4) It is preferable to use 2,2'-bis(trifluoromethyl)benzidine represented by -1) or 3,3'-bis(trifluoromethyl)benzidine represented by the following formula (4-2), in particular It is preferable to use 2,2'-bis(trifluoromethyl)benzidine.

[Formula 27]

In addition, the polyimide used in the present invention is an alicyclic tetracarboxylic acid dianhydride component containing tetracarboxylic dianhydride represented by the above formula (C1), and a diamine component containing diamine represented by formula (A1). When a monomer unit derived from, for example, a monomer unit represented by formula (1) and a monomer unit represented by formula (2), has another monomer unit represented by formula (3), formula (1) ), the polyimide containing each monomer unit represented by formula (2) and formula (3) is represented by the following formula (5) in addition to the above-described two types of tetracarboxylic dianhydride as a tetracarboxylic acid dianhydride component. In addition to the tetracarboxylic dianhydride to be obtained and the diamine represented by the formula (4) as a diamine component, it is obtained by polymerizing the diamine represented by the following formula (6) in an organic solvent to imidize the resulting polyamic acid.

[Formula 28]

A in the above formula (5) and B in the formula (6) represent the same meaning as A and B in the above formula (3), respectively.

Specifically, as the tetracarboxylic dianhydride represented by formula (5), pyromellitic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3,3',4, 4'-benzophenonetetracarboxylic dianhydride, 3,3',4,4'-diphenylethertetracarboxylic dianhydride, 3,3',4,4'-diphenylsulfonetetracarboxylic dianhydride, 4 ,4'-(hexafluoroisopropylidene)diphthalic dianhydride, 11,11-bis(trifluoromethyl)-1H-difluoro[3,4-b:3',4'-i] Santene-1,3,7,9-(11H-tetraone), 6,6'-bis(trifluoromethyl)-[5,5'-biisobenzofuran]-1,1',3,3 '-Tetraone, 4,6,10,12-tetrafluorodipro[3,4-b:3',4'-i]dibenzo[b,e][1,4]dioxin-1, 3,7,9-tetraone, 4,8-bis(trifluoromethoxy)benzo[1,2-c:4,5-c']difuran-1,3,5,7-tetraone, and N,N'-[2,2'-bis(trifluoromethyl)biphenyl-4,4'-diyl]bis(1,3-dioxo-1,3-dihydroisobenzofuran-5-car Aromatic tetracarboxylic acids such as boamide); 1,2-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1 ,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,3,4-cyclohexanetetracarboxylic dianhydride, and 3,4-dicarboxy-1,2,3,4-tetrahydro- Alicyclic tetracarboxylic dianhydrides such as 1-naphthalenesuccinic dianhydride; And, aliphatic tetracarboxylic dianhydrides, such as 1,2,3,4-butanetetracarboxylic dianhydride, are mentioned, but are not limited to these.

Among these, tetracarboxylic dianhydride is preferable where A in formula (5) is a tetravalent group represented by any one of formulas (A-1) to (A-4), that is, 11,11-bis(trifluoro Romethyl)-1H-difluoro[3,4-b:3',4'-i]xanthene-1,3,7,9-(11H-tetraone), 6,6'-bis(tri Fluoromethyl)-[5,5'-biisobenzofuran]-1,1',3,3'-tetraone, 4,6,10,12-tetrafluorodipro[3,4-b: 3',4'-i]dibenzo[b,e][1,4]dioxine-1,3,7,9-tetraone, and 4,8-bis(trifluoromethoxy)benzo[1, 2-c:4,5-c']difuran-1,3,5,7-tetraone is mentioned as a preferable compound.

Further, examples of the diamine represented by formula (6) include 2-(trifluoromethyl)benzene-1,4-diamine, 5-(trifluoromethyl)benzene-1,3-diamine, and 5-( Trifluoromethyl)benzene-1,2-diamine, 2,5-bis(trifluoromethyl)-benzene-1,4-diamine, 2,3-bis(trifluoromethyl)-benzene-1,4 -Diamine, 2,6-bis(trifluoromethyl)-benzene-1,4-diamine, 3,5-bis(trifluoromethyl)-benzene-1,2-diamine, tetrakis(trifluoromethyl) )-1,4-phenylenediamine, 2-(trifluoromethyl)-1,3-phenylenediamine, 4-(trifluoromethyl)-1,3-phenylenediamine, 2-methoxy-1 ,4-phenylenediamine, 2,5-dimethoxy-1,4-phenylenediamine, 2-hydroxy-1,4-phenylenediamine, 2,5-dihydroxy-1,4-phenylenediamine , 2-fluorobenzene-1,4-diamine, 2,5-difluorobenzene-1,4-diamine, 2-chlorobenzene-1,4-diamine, 2,5-dichlorobenzene-1,4- Diamine, 2,3,5,6-tetrafluorobenzene-1,4-diamine, 4,4'-(perfluoropropane-2,2-diyl)dianiline, 4,4'-oxybis[3 -(Trifluoromethyl)aniline], 1,4-bis(4-aminophenoxy)benzene, 1,3'-bis(4-aminophenoxy)benzene, 1,4-bis(3-aminophenoxy) )Benzene, benzidine, 2-methylbenzidine, 3-methylbenzidine, 2-(trifluoromethyl)benzidine, 3-(trifluoromethyl)benzidine, 2,2'-dimethylbenzidine (m-tolidine), 3 ,3'-dimethylbenzidine (o-tolidine), 2,3'-dimethylbenzidine, 2,2'-dimethoxybenzidine, 3,3'-dimethoxybenzidine, 2,3'-dimethoxybenzidine, 2, 2'-dihydroxybenzidine, 3,3'-dihydroxybenzidine, 2,3'-dihydroxybenzidine, 2,2'-difluorobenzidine, 3,3'-difluorobenzidine, 2, 3'-difluorobenzidine, 2,2'-dichlorobenzidine, 3,3'-dichlorobenzidine, 2,3'-dichlorobenzidine, 4,4'-diaminobenzanilide, 4-aminophenyl-4'- Aminobenzoate, octafluorobenzidine, 2,2',5,5'-tetramethylbenzidine, 3,3',5,5'-tetramethylbenzidine, 2,2',5,5'-tetrakis ( Trifluoromethyl)benzy Dean, 3,3',5,5'-tetrakis(trifluoromethyl)benzidine, 2,2',5,5'-tetrachlorobenzidine, 4,4'-bis(4-aminophenoxy) ratio Phenyl, 4,4'-bis(3-aminophenoxy)biphenyl, 4,4'-{[3,3"-bis(trifluoromethyl)-(1,1':3',1"- Terphenyl)-4,4”-diyl]-bis(oxy)}dianiline, 4,4'-{[(perfluoropropane-2,2-diyl)bis(4,1-phenylene)]bis Aromatic diamines such as (oxy)}dianiline and 1-(4-aminophenyl)-2,3-dihydro-1,3,3-trimethyl-1H-indene-5 (or 6)amine; 4,4'-methylenebis(cyclohexylamine), 4,4'-methylenebis(3-methylcyclohexylamine), isophoronediamine, trans-1,4-cyclohexanediamine, cis-1,4-cyclo Hexanediamine, 1,4-cyclohexanebis(methylamine), 2,5-bis(aminomethyl)bicyclo[2.2.1]heptane, 2,6-bis(aminomethyl)bicyclo[2.2.1]heptane , 3,8-bis(aminomethyl)tricyclo[5.2.1.0]decane, 1,3-diaminoadamantane, 2,2-bis(4-aminocyclohexyl)propane, 2,2-bis(4- Aminocyclohexyl) hexafluoropropane, 1,3-propanediamine, 1,4-tetramethylenediamine, 1,5-pentamethylenediamine, 1,6-hexamethylenediamine, 1,7-heptamethylenediamine, 1, And aliphatic diamines such as 8-octamethylenediamine and 1,9-nonamethylenediamine, but are not limited thereto.

Among these, aromatic diamines in which B in formula (6) is a divalent group represented by any one of formulas (B-1) to (B-11) are preferable, that is, 2,2'-bis(trifluoromethoxy )-(1,1'-biphenyl)-4,4'-diamine [alias: 2,2'-dimethoxybenzidine], 4,4'-(perfluoropropane-2,2-diyl) dianiline , 2,5-bis(trifluoromethyl)benzene-1,4-diamine, 2-(trifluoromethyl)benzene-1,4-diamine, 2-fluorobenzene-1,4-diamine, 4, 4'-oxybis[3-(trifluoromethyl)aniline], 2,2',3,3',5,5',6,6'-octafluoro[1,1'-biphenyl]- 4,4'-diamine [alias: octafluorobenzidine], 2,3,5,6-tetrafluorobenzene-1,4-diamine, 4,4'-{[3,3"-bis(trifluoro Romethyl)-(1,1':3',1"-terphenyl)-4,4"-diyl]-bis(oxy)}dianiline, 4,4'-{[(perfluoropropane-2 ,2-diyl)bis(4,1-phenylene)]bis(oxy)}dianiline, and 1-(4-aminophenyl)-2,3-dihydro-1,3,3-trimethyl-1H- Inden-5 (or 6) amine is mentioned as a preferable diamine.

<Synthesis of polyamic acid>

In a preferred embodiment of the polyimide used in the present invention, as described above, a tetracarboxylic acid dianhydride component containing an alicyclic tetracarboxylic acid dianhydride represented by the above formula (C1), and the above formula (A1) It is obtained by imidizing a polyamic acid obtained by reacting a diamine component containing a fluorinated aromatic diamine represented by.

Specifically, for example, as a suitable example, bicyclo[2.2.2]octane-2,3,5,6-tetracarboxylic dianhydride, and optionally 1,2,3,4-cyclobutanetetra A tetracarboxylic acid dianhydride component consisting of a carboxylic acid dianhydride, and further, a tetracarboxylic acid dianhydride represented by the above formula (5), if necessary, a diamine represented by the above formula (4), and, if necessary, the above formula (6) It is obtained by polymerizing a diamine component composed of a diamine component represented by in an organic solvent to imidize the obtained polyamic acid.

The reaction to the polyamic acid from the above two components is advantageous in that it can relatively easily proceed in an organic solvent and no by-products are generated.

Although the addition ratio (molar ratio) of the diamine component in the reaction between these tetracarboxylic dianhydride components and the diamine component is appropriately set in consideration of the molecular weight of the polyamic acid, and further, the polyimide obtained by imidization thereafter. , With respect to the diamine component 1, usually, the tetracarboxylic dianhydride component can be about 0.8 to 1.2, for example, about 0.9 to 1.1, preferably about 0.95 to 1.02. Similar to a normal polycondensation reaction, the molecular weight of the resulting polyamic acid increases as the molar ratio approaches 1.0.

The organic solvent used in the reaction of the tetracarboxylic dianhydride component and the diamine component is not particularly limited as long as it does not adversely affect the reaction and the resulting polyamic acid is dissolved. The specific example is given below.

For example, m-cresol, 2-pyrrolidone, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-vinyl-2-pyrrolidone, N,N-dimethylform Amide, N,N-dimethylacetamide, 3-methoxy-N,N-dimethylpropylamide, 3-ethoxy-N,N-dimethylpropylamide, 3-propoxy-N,N-dimethylpropylamide, 3 -Isopropoxy-N,N-dimethylpropylamide, 3-butoxy-N,N-dimethylpropylamide, 3-sec-butoxy-N,N-dimethylpropylamide, 3-tert-butoxy-N, N-dimethylpropylamide, γ-butyrolactone, N-methylcaprolactam, dimethylsulfoxide, tetramethylurea, pyridine, dimethylsulfone, hexamethylsulfoxide, isopropyl alcohol, methoxymethylpentanol, dipentene, ethyl Amyl ketone, methyl nonyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl ketone, methyl cellosolve, ethyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, butyl carbitol, ethylcar Bitol, ethylene glycol, ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol-tert-butyl ether, dipropylene glycol monomethyl Ether, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, Dipropylene glycol monopropyl ether, dipropylene glycol monoacetate monopropyl ether, 3-methyl-3-methoxybutyl acetate, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl iso Butyl ether, diisobutylene, amyl acetate, butyl butyrate, butyl ether, diisobutyl ketone, methylcyclohexene, dipropyl ether, dihexyl ether, dioxane, n-hexane, n-pentane, n-octane, di Ethyl ether, cyclohexanone, ethylene carbonate, propylene carbonate, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether, pyruvate Acid methyl, ethyl pyruvate, 3-methoxypropionate methyl, 3-ethoxypropionate isopropyl, 3-methoxypropionate ethyl, 3-ethoxypropionic acid, 3-methoxypropionic acid, 3-methoxypropionate propyl, 3-methoxy Butyl oxypropionate, diglyme, and 4-hydroxy-4-methyl-2-pentanone may be mentioned, but are not limited thereto. These may be used alone or in combination of two or more.

Furthermore, even if it is a solvent which does not dissolve the polyamic acid, it can also be used by mixing with the said solvent in the range in which the produced|generated polyamic acid does not precipitate. In addition, since moisture in the organic solvent inhibits the polymerization reaction and furthermore causes hydrolysis of the produced polyamic acid, it is preferable to use dehydration-dried organic solvent as much as possible.

As a method of reacting the tetracarboxylic dianhydride component and the diamine component in an organic solvent, a dispersion or solution in which the diamine component is dispersed or dissolved in an organic solvent is stirred, and the tetracarboxylic dianhydride component is added as it is, or Or a method of adding a tetracarboxylic acid component dispersed or dissolved in an organic solvent, on the contrary, a method of adding a diamine component to a dispersion or solution in which the tetracarboxylic acid dianhydride component is dispersed or dissolved in an organic solvent, and tetracarboxylic acid A method of alternately adding an anhydride component and a diamine compound component, and the like, and any of these may be used.

In addition, when the tetracarboxylic acid dianhydride component and/or the diamine component are made of a plurality of compounds, they may be reacted in a premixed state, individually sequentially reacted, or further individually reacted low molecular weight compounds. It can also be mixed and reacted to obtain a high molecular weight.

The temperature during the synthesis of the polyamic acid may be appropriately set in the range from the melting point to the boiling point of the solvent to be used. For example, an arbitrary temperature of -20°C to 150°C can be selected, but -5°C to 150°C, usually about 0 to 150°C, preferably about 0 to 140°C.

The reaction time depends on the reaction temperature or the reactivity of the raw material and cannot be defined collectively, but is usually about 1 to 100 hours.

In addition, the reaction can be carried out at an arbitrary concentration. If the concentration is too low, it becomes difficult to obtain a high molecular weight polymer, and if the concentration is too high, the viscosity of the reaction solution becomes too high and uniform stirring becomes difficult. The total concentration in the reaction solution of the anhydride component and the diamine component is preferably 1 to 50% by mass, more preferably 5 to 40% by mass. The initial reaction is carried out at a high concentration, and then an organic solvent may be added.

<Imidation of polyamic acid>

As a method of imidizing the polyamic acid, thermal imidization in which the solution of polyamic acid is heated as it is, and catalytic imidization in which a catalyst is added to the solution of polyamic acid are exemplified.

When the polyamic acid is thermally imidized in a solution, the temperature is 100°C to 400°C, preferably 120°C to 250°C, and it is preferable to perform while removing the water generated by the imidation reaction out of the system.

Chemical (catalytic) imidization of polyamic acid can be performed by adding a basic catalyst and an acid anhydride to a solution of polyamic acid, and stirring the system at a temperature condition of -20 to 250°C, preferably 0 to 180°C. have.

The amount of the basic catalyst is 0.5 to 30 mole times, preferably 1.5 to 20 mole times of the amic acid group of the polyamic acid, and the amount of the acid anhydride is 1 to 50 mole times, preferably 2 to 30 mole times of the amic acid group of the polyamic acid.

Examples of the basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine, trioctylamine, and 1-ethylpiperidine, among which pyridine and 1-ethylpiperidine are used to advance the reaction. It is preferable because it has moderate basicity.

The imidation rate by catalytic imidization can be controlled by adjusting the amount of catalyst, reaction temperature, and reaction time.

In the polyimide used in the present invention, the dehydration/closing rate (imidation rate) of the amic acid group does not necessarily need to be 100%, and can be arbitrarily adjusted according to the use or purpose. It is particularly preferably 50% or more.

In the present invention, the reaction solution of the imidization can be used as it is to prepare an organic-inorganic hybrid resin composition without going through the process of polymer recovery described later. In that case, after filtering the reaction solution, the filtrate itself Or, it is preferable to use the filtrate diluted or concentrated in the organic-inorganic hybrid resin composition. In the case of filtering in this way, it is possible to reduce the incorporation of impurities that may cause deterioration in heat resistance, flexibility, or linear expansion coefficient characteristics of the resulting organic-inorganic hybrid resin thin film.

In addition, the polyimide used in the present invention is the strength of a resin thin film (organic-inorganic hybrid resin thin film) obtained from an organic-inorganic hybrid resin composition, and workability when forming a resin thin film made of an organic-inorganic hybrid resin composition on a supporting substrate, etc. , In consideration of the uniformity of the organic-inorganic hybrid resin thin film, it is preferable that the weight average molecular weight (Mw) in terms of polystyrene by gel permeation chromatography (GPC) is 5,000 to 200,000.

<Recovery of polymer>

When the polymer component is recovered from the reaction solution of polyamic acid and polyimide, and this is used for the preparation of polyimide, furthermore, for preparing the organic-inorganic hybrid resin composition, the reaction solution may be added to a poor solvent to precipitate. Poor solvents used for precipitation include methanol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene, isopropanol, and water. The polymer injected into the poor solvent and precipitated can be recovered by filtration, and then dried at room temperature or heated under normal pressure or reduced pressure.

Further, by re-dissolving the polymer recovered by precipitation in an organic solvent and repeating the reprecipitation recovery operation 2 to 10 times, impurities in the polymer can be reduced. When three or more types of poor solvents, such as alcohols, ketones, and hydrocarbons, are used as the poor solvent at this time, since the efficiency of purification is further increased, it is preferable.

The organic solvent for dissolving the resin component in the reprecipitation recovery step is not particularly limited. Specific examples include N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam, 2-pyrrolidone, N-ethylpyrrolidone, N-vinylpyrrolidone, dimethylsulfoxide, tetramethylurea, pyridine, dimethylsulfone, hexamethylsulfoxide, γ-butyrolactone, 1,3-dimethyl-imidazolidinone, dipentene, ethyl amylketone, methyl Nonyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl ketone, cyclohexanone, ethylene carbonate, propylene carbonate, diglyme, 4-hydroxy-4-methyl-2-pentanone, and the like. These solvents can also be used by mixing two or more types.

[Other inorganic fine particles]

The organic-inorganic hybrid resin composition of the present invention may contain inorganic fine particles other than the inorganic fine particles described above, that is, other inorganic fine particles not modified with a specific alkoxysilane compound. In that case, the content of other inorganic fine particles not modified with a specific alkoxysilane compound is based on the sum of the inorganic fine particles as component (A) of the present application and other inorganic fine particles not modified with a specific alkoxysilane compound, It is 50 mass%-0 mass %, Preferably it is 20 mass%-0 mass %.

[Crosslinking agent]

The organic-inorganic hybrid resin composition of the present invention may further contain a crosslinking agent. The crosslinking agent used herein is a compound consisting of only hydrogen atoms, carbon atoms, and oxygen atoms, or compounds consisting only of hydrogen atoms, carbon atoms, nitrogen atoms and oxygen atoms, and is a hydroxy group, an epoxy group, and 1 to 5 carbon atoms. It is a crosslinking agent composed of a compound having two or more groups selected from the group consisting of alkoxy groups and further having a cyclic structure. By using such a crosslinking agent, it is possible to realize an organic-inorganic hybrid resin composition having superior solvent resistance and excellent reproducibility, as well as improved storage stability, a resin thin film suitable for a substrate for flexible devices.

Among them, the total number of hydroxy groups, epoxy groups, and alkoxy groups having 1 to 5 carbon atoms per compound in the crosslinking agent is preferably 3 or more from the viewpoint of achieving good reproducibility of the solvent resistance of the resulting resin thin film, From the viewpoint of realizing the flexibility of the obtained resin thin film with good reproducibility, it is preferably 10 or less, more preferably 8 or less, and even more preferably 6 or less.

Specific examples of the ring structure possessed by the crosslinking agent include aryl rings such as benzene, nitrogen-containing heteroaryl rings such as pyridine, pyrazine, pyrimidine, pyridazine, 1,3,5-triazine, cyclopentane, cyclohexane, Cycloalkane rings such as cycloheptane, piperidine, piperazine, hexahydropyrimidine, hexahydropyridazine, and cyclic amines such as hexahydro-1,3,5-triazine, and the like.

The number of cyclic structures per compound in the crosslinking agent is not particularly limited as long as it is 1 or more, but 1 or 2 is preferable from the viewpoint of securing solubility of the crosslinking agent in a solvent to obtain a resin thin film having high flatness.

On the other hand, when two or more ring structures are present, the ring structures may be condensed, and alkane-di having 1 to 5 carbon atoms such as methylene group, ethylene group, trimethylene group, propane-2,2-diyl group, etc. Ring structures may be bonded to each other through a connector such as a diary.

The molecular weight of the crosslinking agent is not particularly limited as long as it has crosslinking ability and is dissolved in the solvent to be used, but it is preferable in consideration of the solvent resistance of the obtained resin thin film, the solubility of the crosslinking agent itself in an organic solvent, availability, and price It is preferably about 100 to 500, more preferably about 150 to 400.

The crosslinking agent may further have a group derived from a hydrogen atom, a carbon atom, a nitrogen atom, and an oxygen atom, such as a ketone group, an ester group (bond), and the like.

As a preferable example as a crosslinking agent, a compound represented by any one of the following formulas (K1) to (K5) may be mentioned, and as one of the preferred embodiments of formula (K4), a compound represented by formula (K4-1) As one of the preferable aspects of (K5), the compound represented by formula (5-1) is mentioned, respectively.

[Chemical Formula 29]

In the above formula, each A ¹ and A ² each independently represent an alkane-diyl group having 1 to 5 carbon atoms such as a methylene group, an ethylene group, a trimethylene group, and a propane-2,2-diyl group, and Especially, as A ¹ , a methylene group and an ethylene group are preferable, and a methylene group is more preferable, and as A ² , a methylene group and a propane-2,2-diyl group are preferable.

In the formulas (K1) to (K5), each of X is independently a hydroxy group, an epoxy group (oxa-cyclopropyl group), or a methoxy group, an ethoxy group, a 1-propyloxy group, an isopropyloxy group, An alkoxy group having 1 to 5 carbon atoms, such as a 1-butyloxy group and a t-butyloxy group, is shown.

Especially, considering the availability and price of a crosslinking agent, X is preferably an epoxy group in formulas (K1) and (K5), and an alkoxy group having 1 to 5 carbon atoms in formulas (K2) and (K3) It is preferable, and in formula (K4), a hydroxy group is preferable.

In formula (K4), each n represents the number of -(A ¹ -X) groups bonded to the benzene ring, and independently of each other an integer of 1 to 5, preferably 2 to 3, more preferably 3 to be.

In each compound, it is preferable that all of each A ¹ are the same group, and it is preferable that all of each X are the same group.

The compounds represented by the formulas (K1) to (K5) are skeletal compounds such as an aryl compound, heteroaryl compound, and cyclic amine having the same ring structure as the ring structure among these compounds, and an epoxy alkyl halide compound, an alkoxy halide compound And the like can be obtained by reacting by carbon-carbon coupling reaction or N-alkylation reaction, or by hydrolyzing the resulting alkoxy moiety.

As the crosslinking agent, a commercial item may be used, or a compound synthesized by a known synthesis method may be used.

Commercially available products include CYMEL (registered trademark) 300, 301, 303LF, 303ULF, 304, 350, 3745, XW3106, MM-100, 323, 325, 327, 328, dong 385, 370, dong 373, 380, 1116, 1130, 1133, 1141, 1161, 1168, 3020, 202, 203, 1156, MB-94, MB-96 , East MB-98, East 247-10, East 651, East 658, East 683, East 688, East 1158, East MB-14, East MI-12-I, East MI-97-IX, East U-65, East UM-15, East U-80, East U-21-511, East U-21-510, East U-216-8, East U-227-8, East U-1050-10, East U-1052- 8, East U-1054, East U-610, East U-640, East UB-24-BX, East UB-26-BX, East UB-90-BX, East UB-25-BE, East UB-30- B, East U-662, East U-663, East U-1051, East UI-19-I, East UI-19-IE, East UI-21-E, East UI-27-EI, East U-38- I, Building UI-20-E, Building 659, Building 1123, Building 1125, Building 5010, Building 1170, Building 1172, Building NF3041, Building NF2000, etc. (above, manufactured by Allnex); TEPIC (registered trademark) V, copper S, copper HP, copper L, copper PAS, copper VL, copper UC (above, manufactured by Nissan Chemical Industries, Ltd.), TM-BIP-A (manufactured by Asahi Organic Materials Industries, Ltd.) , 1,3,4,6-tetrakis (methoxymethyl) glycoluril (hereinafter abbreviated as TMG) (manufactured by Tokyo Chemical Industry Co., Ltd.), 4,4'-methylenebis (N,N-digly Cydilaniline) (manufactured by Aldrich), HP-4032D, HP-7200L, HP-7200, HP-7200H, HP-7200HH, HP-7200HHH, HP-4700, HP-4770, HP-5000, HP-6000, HP -4710, EXA-4850-150, EXA-4850-1000, EXA-4816, HP-820 (DIC Co., Ltd.), TG-G (Shikoku Chemical Co., Ltd.), and the like.

Hereinafter, although preferable specific examples are given as a crosslinking agent, it is not limited to these.

[Formula 30]

The blending amount of the crosslinking agent is suitably determined depending on the type of crosslinking agent, so it cannot be specified collectively, but usually, the flexibility of the obtained resin thin film with respect to the mass of the polyimide or the total mass of the polyimide and the inorganic fine particles. It is 50 mass% or less, preferably 100 mass% or less, from the viewpoint of securing of and suppression of brittleness, and 0.1 mass% or more, preferably 1 mass% or more, from the viewpoint of securing the solvent resistance of the obtained resin thin film. .

[(C): Organic solvent]

The organic-inorganic hybrid resin composition of the present invention contains an organic solvent in addition to the polyimide, inorganic fine particles whose surface has been modified with a specific alkoxysilane, any other inorganic fine particles, and a crosslinking agent. The organic solvent is not particularly limited, and examples thereof include the same as the specific examples of the reaction solvent used in the preparation of the polyamic acid and polyimide. More specifically, N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, N-ethyl-2- Pyrrolidone, γ-butyrolactone, and the like. On the other hand, the organic solvent may be used alone or in combination of two or more.

Among these, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, and γ-butyrolactone are preferable in consideration of obtaining a resin thin film having high flatness with good reproducibility.

[Organic-inorganic hybrid resin composition]

The present invention includes (A) inorganic fine particles whose surface has been modified with a specific alkoxysilane, (B) the polyimide, and (C) an organic solvent, and if necessary, other inorganic fine particles such as silicon dioxide, crosslinking agents, etc. It is an organic-inorganic hybrid resin composition containing. Here, the organic-inorganic hybrid resin composition of the present invention is uniform and does not show phase separation.

In the organic-inorganic hybrid resin composition of the present invention, the blending ratio of (A) inorganic fine particles whose surface has been modified with a specific alkoxysilane and (B) the polyimide is in terms of mass ratio, (A) inorganic fine particles: (B) polyimide It is preferable that it is mid=10:1-1:10, More preferably, it is 8:2-2:8, for example, 7:3-3:7, or it can be 5:5-9:1 . On the other hand, when other inorganic fine particles not modified with a specific alkoxysilane compound are included, the mass ratio can be considered as including other inorganic fine particles in the mass of (A) inorganic fine particles. The content of other inorganic fine particles not modified with the alkoxysilane compound is 50% by mass to 0 based on the total of the inorganic fine particles as component (A) of the present application and other inorganic fine particles not modified with a specific alkoxysilane compound. It is mass %, preferably 20 mass%-0 mass %.

In addition, the solid amount in the organic-inorganic hybrid resin composition of the present invention is usually in the range of 0.5 to 30% by mass, but from the viewpoint of the uniformity of the film, it is preferably 5% by mass or more and 20% by mass or less. Meanwhile, the solid content refers to the remaining components excluding the solvent from all components constituting the organic-inorganic hybrid resin composition.

On the other hand, the viscosity of the organic-inorganic hybrid resin composition is determined appropriately in consideration of the coating method to be used, the thickness of the resin thin film to be produced, and the like, but is usually 1 to 50,000 mPa·s at 25°C.

In order to impart processing characteristics and various functions to the organic-inorganic hybrid resin composition of the present invention, various organic or inorganic low-molecular or high-molecular compounds may be blended. For example, catalysts, defoaming agents, leveling agents, surfactants, dyes, plasticizers, fine particles, coupling agents, sensitizers, and the like can be used. For example, the catalyst may be added for the purpose of lowering the retardation or linear expansion coefficient of the resin thin film.

In the organic-inorganic hybrid resin composition of the present invention, the polyimide obtained by the above-described method, inorganic fine particles modified on the surface with the specific alkoxysilane compound described above, and other inorganic fine particles such as silicon dioxide, crosslinking agents, etc. It can be obtained by dissolving in a solvent, and to the reaction solution after the preparation of polyimide, inorganic fine particles or a solution thereof whose surface has been modified with the specific alkoxysilane compound described above are added, and further silicon dioxide, crosslinking agent, etc. are added as necessary. And, if necessary, the organic solvent may be further added.

[Resin thin film and substrate for flexible device]

The organic-inorganic hybrid resin composition of the present invention described above removes the organic solvent by applying it to a substrate, drying and heating, and has excellent heat resistance, low retardation, excellent flexibility, and further excellent transparency (high Light transmittance: For example, light transmittance at 400 nm of 80% or more, low yellowness: For example, a haze value of 2% or less) A thin resin film can be obtained, and while maintaining these excellent performances, mechanical A resin thin film useful as a substrate for flexible devices that can be peeled off by peeling can be obtained.

And a resin thin film formed from the organic-inorganic hybrid resin composition, and a substrate for a flexible device, i.e., inorganic fine particles modified on the surface with the polyimide and the above-described specific alkoxysilane compound, inorganic fine particles such as silicon dioxide, and a crosslinking agent if necessary A substrate for a flexible device containing the like, that is, a substrate for a flexible device comprising a cured product of the organic-inorganic hybrid resin composition of the present invention is also an object of the present invention.

As a base material used for manufacturing a flexible device substrate (resin thin film), for example, plastics (polycarbonate, polymethacrylate, polystyrene, polyester, polyolefin, epoxy, melamine, triacetylcellulose, ABS, AS, novo Nene resin, etc.), metal, stainless steel (SUS), wood, paper, glass, silicon wafer, slate, and the like.

Particularly, when applying as a substrate for a flexible device, it is preferable that the substrate to be applied is glass or a silicon wafer from the viewpoint of being able to use existing equipment, and the substrate for a flexible device obtained is glass because it exhibits good peelability. More preferable. On the other hand, the coefficient of linear expansion of the substrate to be applied is preferably 40 ppm/°C or less, more preferably 30 ppm/°C or less from the viewpoint of warpage of the substrate after coating.

In order to form a release layer on the substrate, a known method may be used. That is, a known release layer forming composition containing an aromatic polyimide, polybenzoxazole, etc. is applied on a substrate and then calcined so that the temperature reaches more than 450°C by a known method, thereby forming a release layer on the substrate. Can be formed. They can apply, for example, International Publication No. 2017/204178, International Publication No. 2017/204182, International Publication No. 2017/204186, etc., and the composition and peeling layer described as a composition for forming a peeling layer and a peeling layer.

The coating method of the organic-inorganic hybrid resin composition on the substrate or on the release layer formed on the substrate is not particularly limited, but for example, a cast coating method, a spin coating method, a blade coating method, a dip coating method, A roll coating method, a bar coating method, a die coating method, an inkjet method, a printing method (convex plate, concave plate, flat plate, screen printing, etc.), and the like, and these can be suitably used depending on the purpose.

The heating temperature is preferably 350°C or less. If it exceeds 350°C, the resulting thin resin film becomes brittle, and in particular, a thin resin film suitable for use in a display substrate may not be obtained.

In addition, considering the heat resistance and linear expansion coefficient characteristics of the obtained resin thin film, the applied organic-inorganic hybrid resin composition is heated at 40°C to 100°C for 5 minutes to 2 hours, and then the heating temperature is raised step by step as it is, and finally 175 It is preferable to heat at more than ℃ ~ 350 ℃ for 30 minutes to 2 hours. In this way, by heating at a temperature of two or more steps of drying the solvent and promoting molecular orientation, it is possible to exhibit low thermal expansion characteristics with better reproducibility.

In particular, the applied organic-inorganic hybrid resin composition is heated at 40°C to 100°C for 5 minutes to 2 hours, and then at over 100°C to 175°C for 5 minutes to 2 hours, followed by more than 175°C to 350°C for 5 minutes. It is preferable to heat for ~ 2 hours.

As a device used for heating, a hot plate, an oven, etc. are mentioned, for example. The heating atmosphere may be under air or under an inert gas such as nitrogen, and may be under normal pressure or under reduced pressure, and different pressures may be applied in each step of heating.

Although the thickness of the resin thin film is appropriately determined in consideration of the type of flexible device within the range of about 1 to 200 μm, especially when it is assumed that it is used as a substrate for a flexible display, it is usually about 1 to 60 μm, preferably It is about 5 to 50 μm, and a thin resin film of a desired thickness is formed by adjusting the thickness of the coating film before heating.

On the other hand, the method of peeling the thus formed resin thin film from the substrate is not particularly limited, and a method of cooling the resin thin film with the substrate and peeling the thin film with a sheath, or a method of peeling by applying tension through a roll, etc. Can be mentioned.

The resin thin film according to one preferred embodiment of the present invention thus obtained has high transparency that the light transmittance at 400 nm is 80% or more and the light transmittance at 550 nm is 90% or more, 2% or less, preferably 1.5%. It is possible to realize a low degree of yellowness such as the following haze value.

Furthermore, this resin thin film may have a low value of 25 ppm/°C or less, particularly 5 ppm/°C to 25 ppm/°C, and has excellent dimensional stability when heated, for example, at 50°C to 200°C. .

In addition, this resin thin film has a birefringence when the wavelength of incident light is 590 nm, that is, two birefringences when viewed from a cross section in the thickness direction (the difference between the two refractive indexes in the plane and the refractive index in the thickness direction). each layer multiplied by the thickness and the second thickness direction retardation of the phase difference appear as an average of the retardation R _th Features that are small can be obtained.

The resin thin film described above satisfies each condition required as a base film for a flexible device substrate in terms of having the above characteristics, and can be particularly suitably used as a base film for a flexible device, particularly a substrate for a flexible display.

As another aspect of the present application, a method of manufacturing a substrate for a flexible device is provided.

This way,

a) forming a release layer on a supporting substrate such as a glass substrate;

b) forming a resin thin film serving as a substrate for a flexible device by using the organic-inorganic hybrid resin composition of the present invention on this release layer; And

c) removing the resin thin film from the peeling layer to obtain a flexible device substrate;

By having a, a substrate for a flexible device can be obtained.

As shown in Fig. 1, the step c) is a step of peeling the resin thin film at the interface between the de-bonding layer and the resin thin film (PI/silica film) serving as the flexible device substrate.

The release layer can be formed from a known release layer forming composition containing the aromatic polyimide or polybenzoxazole described above.

Example

Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited to the following examples.

The meanings of the abbreviations used in the following examples are as follows.

<acid dianhydride>

BODAxx: Bicyclo[2,2,2]octane-2,3,5,6-tetracarboxylic dianhydride

CBDA: 1,2,3,4-cyclobutanetetracarboxylic dianhydride

PMDA: pyromellitic dianhydride

<Diamine>

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

p-PDA: p-phenylenediamine

<Organic solvent>

GBL: γ-butyrolactone

NMP: N-methyl-2-pyrrolidone

On the other hand, in Examples, the apparatus and conditions used for preparation of a sample and analysis and evaluation of physical properties are as follows.

1) Measurement of number average molecular weight and weight average molecular weight

The number average molecular weight (hereinafter, abbreviated as Mn) and weight average molecular weight (hereinafter, abbreviated as Mw) of the polymer are: Apparatus: Showdex GPC-101, columns: KD803 and KD805, column temperature : 50°C, elution solvent: DMF, flow rate: 1.0 ml/min, calibration curve: measured under the conditions of standard polystyrene.

2) film thickness

The film thickness of the obtained resin thin film was measured with a thickness gauge manufactured by Techrock Co., Ltd.

3) Coefficient of linear expansion (CTE)

Using TMA Q400 manufactured by TA Instruments, a thin film was cut into a size of 5 mm in width and 16 mm in length, first heated to 50 to 350°C by heating at 10°C/min (first heating), and then at 10°C/min. After cooling to 50°C by lowering the temperature, the coefficient of linear expansion (CTE [ppm/) at 50°C to 200°C of the second heating when the temperature is raised at 10°C/min and heated to 50 to 420°C (second heating) °C]). On the other hand, through the first heating, cooling, and second heating, a load of 0.05 N was applied.

4) Thermal decomposition temperature 5% weight reduction temperature (Td _5% )

The 5% weight loss temperature (Td _5% [°C]) was determined by measuring about 5 to 10 mg of a thin film in nitrogen at 10°C/min to 50 to 800°C using TGA Q500 manufactured by TA Instruments.

5) Light transmittance (transparency) (T _400nm , T _550nm ) and CIE b value (CIE b ^* )

The light transmittance (T _400nm , T _550nm [%]) and CIE b value (CIE b ^* ) at wavelengths of 400 nm and 550 _nm were obtained using a SA4000 spectrometer manufactured by Japan Electronics Co., Ltd. , Was measured.

6) Retardation (R _th )

The thickness direction retardation (R _th ) was measured at room temperature using KOBURA 2100ADH, manufactured by Oji Measuring Instruments Co., Ltd.

On the other hand, the thickness direction retardation R _th is calculated by the following equation.

R _th =[(Nx+Ny)/2-Nz]×d=[(ΔNxz×d)+(ΔNyz×d)/2

Nx, Ny: two orthogonal refractive indices in the plane (Nx>Ny, Nx is also called slow axis, Ny is also called fast axis)

Nz: refractive index in the thickness (vertical) direction with respect to the plane

d: film thickness

ΔNxy: The difference between the two refractive indices in the plane (Nx-Ny) (birefringence)

ΔNxz: The difference between the refractive index Nx in the plane and the refractive index Nz in the thickness direction (birefringence)

ΔNyz: The difference between the refractive index Ny in the plane and the refractive index Nz in the thickness direction (birefringence)

7) The polyimide was dried in a Drv 320 vacuum oven manufactured by Advantech.

[1] Synthesis example

Synthesis Example 1: Synthesis of polyimide A (PI-A) and preparation of 7 wt% solution

[Formula 31]

Into a 250 mL reaction 3-neck flask equipped with a nitrogen inlet/outlet, a mechanical stirrer, and a cooler, 25.6 g (0.08 mol) of TFMB was placed. Then, 173 g of GBL was added and stirring was started. After the diamine was completely dissolved in the solvent, immediately after that, 10.0 g (0.04 mol) of the stirred BODAxx, 7.84 g (0.04 mol) of CBDA and 43.4 g of GBL were added, followed by heating to 140° C. under nitrogen. Then, 0.35 g of 1-ethylpiperidine was added into the solution, and heated to 180°C for 7 hours under nitrogen. Finally, the heating was stopped, the reaction solution was diluted to 10%, and the final solution agitation was maintained. The polyimide reaction solution was added to 2000 g of GBL:methanol=50wt%:50wt% mixed solution, stirred for 30 minutes, and then the polyimide solid was filtered to purify the polyimide. And this polyimide solid was stirred in 2000 g of methanol for 30 minutes, and the polyimide solid was filtered. The purification procedure of stirring and filtration of this polyimide solid was repeated three times. The methanol residue in the polyimide was removed by drying in a vacuum oven at 150° C. for 8 hours, and finally, 21.5 g of dried polyimide A was obtained. The yield of polyimide A (PI-A) was 51% (Mw=310,000, Mn=144,300). 7 g of this PI-A was placed in a 500 mL Erlenmeyer flask, and then 93 g of GBL was added, followed by stirring at room temperature for 4 days to obtain a 7 wt% polyimide GBL solution (PI-B).

Synthesis Example 2: Synthesis of varnish for release layer (DBL-1)

1.02 g (9.5 mmol) of p-PDA was dissolved in 26.4 g of NMP. To the obtained solution, PMDA 2.58 g (11.8 mmol) was added and reacted at 23°C for 24 hours in a nitrogen atmosphere. Then, 0.44 g (4.7 mmol) of aniline was added, and the reaction was carried out for an additional 24 hours. The obtained polymer had Mw of 31,500 and a molecular weight distribution of 3.2. NMP 23g was added to this solution, and it stirred at room temperature for 24 hours, and obtained the varnish for peeling layers (DBL-1).

[2] Preparation example

Preparation Example 1: Preparation of a solution containing specific alkoxysilane-modified silica particles (Si-1)

In a 500 mL reaction 3-neck flask equipped with a nitrogen inlet/outlet and a cooler, Quatron PL-1-IPA (manufactured by Fuso Chemical Industry Co., Ltd., registered trademark, particle diameter (in terms of specific surface area) 10 to 15 nm, dispersion medium isopropanol) 200 g ( 13.3%) and 1.644 g of 4-biphenyltrimethoxysilane were added. Then, it heated at 100 degreeC for 17 hours in nitrogen atmosphere. After the reaction was completed, 79.8 g of GBL was added, and isopropanol was distilled off under reduced pressure with an evaporator to obtain a GBL sol solution (Si-1) of silica particles modified with a specific alkoxysilane. 1 g of this solution was heated on an aluminum cup at 200° C. for 2 hours, and the concentration was calculated from the remaining amount. As a result, the concentration was 35 wt%.

Preparation Example 2: Preparation of a solution containing specific alkoxysilane-modified silica particles (Si-2)

In a 100 mL reaction 3-neck flask equipped with a nitrogen inlet/outlet and a cooler, Quatron PL-1-IPA (manufactured by Fuso Chemical Industries, Ltd., registered trademark, particle size (specific surface area conversion) 10 to 15 nm, dispersion medium isopropanol) 50 g ( 13.3%) and 0.206 g of 4-biphenyltrimethoxysilane were added. Then, it heated at 100 degreeC for 22 hours in nitrogen atmosphere. After completion of the reaction, 19.9 g of GBL was added, and isopropanol was distilled off under reduced pressure with an evaporator to obtain a GBL sol solution (Si-2) of silica particles modified with a specific alkoxysilane. 1 g of this solution was heated on an aluminum cup at 200° C. for 2 hours, and the concentration was calculated from the remaining amount, and the concentration was 35 wt%.

Preparation Example 3: Preparation of alkoxysilane-modified silica particle-containing solution (Si-3)

In a 500 mL reaction 3-neck flask equipped with a nitrogen inlet/outlet and a cooler, Quatron PL-1-IPA (manufactured by Fuso Chemical Industry Co., Ltd., registered trademark, particle diameter (in terms of specific surface area) 10 to 15 nm, dispersion medium isopropanol) 200 g ( 13.3%) and 1.13 g of phenyltrimethoxysilane were added. Then, it heated at 100 degreeC for 17 hours in nitrogen atmosphere. After completion of the reaction, 79.8 g of GBL was added, and isopropanol was evaporated under reduced pressure with an evaporator to obtain a GBL sol solution (Si-3) of silica particles modified with alkoxysilane. 1 g of this solution was heated on an aluminum cup at 200° C. for 2 hours, and the concentration was calculated from the remaining amount, and the concentration was 35 wt%.

Preparation Example 4: Preparation of a solution containing silica particles (Si-4)

Quatron PL-1-IPA (Fuso Chemical Industry Co., Ltd. product, registered trademark, particle diameter (specific surface area conversion) 10-15nm, dispersion medium isopropanol) 200g (13.3%) and GBL 79.8g were added to a 500mL eggplant flask, and then distributed. The isopropanol was distilled off under reduced pressure with a separator to obtain a GBL sol solution (Si-4) of alkoxysilane non-aqueous silica particles. 1 g of this solution was heated on an aluminum cup at 200° C. for 2 hours, and the concentration was calculated from the remaining amount, and the concentration was 35 wt%.

[3] formation of a release layer

Using a spin coater (condition: about 30 seconds at a rotation speed of 3,000 rpm), the varnish for a release layer (DBL-1) obtained in Synthesis Example 2 was applied on a 100 mm×100 mm glass substrate (the same hereinafter) as a glass substrate.

Then, the obtained coating film was heated at 80° C. for 10 minutes using a hot plate, and then heated at 300° C. for 30 minutes using an oven, and the heating temperature was raised to 500° C. (10° C./min), By heating again at 500° C. for 10 minutes, a release layer having a thickness of about 0.1 μm was formed on the glass substrate. On the other hand, during heating up, the film-attached substrate was heated in the oven without taking it out of the oven.

[4] Preparation of composition and formation of film

Example 1

To 10 g of a 7 wt% polyimide GBL solution (PI-B) obtained in Synthesis Example 1, 4.66 g of a specific alkoxysilane-modified silica particle-containing solution (Si-1) and 3.27 g of GBL were added, followed by stirring at room temperature for 3 days. Then, it filtered through a 0.45 micron propylene filter, and the target varnish (organic-inorganic hybrid resin composition) was obtained. The obtained varnish was applied on the peeling layer with a bar coater (with a gap of 250 microns), and heated at 100°C for 1 hour using a hot plate. Then, it was heated on a hot plate at 280° C. for 30 minutes to obtain a transparent PI film LI. L1 could be easily peeled from the peeling layer as shown in FIG. 1. Table 1 shows the optical and thermal properties of L1.

Example 2

In place of the above (Si-1), a varnish (organic-inorganic hybrid resin composition) was obtained in the same manner as in Example 1, except that 4.66 g of a specific alkoxysilane-modified silica particle-containing solution (Si-2) was used. It applied on the peeling layer and formed into a film, and the transparent PI film L2 was obtained. Like L1, L2 could be easily peeled from the peeling layer. Table 1 shows the optical and thermal properties of L2.

Example 3

To 10 g of a 7 wt% polyimide GBL solution (PI-B) obtained in Synthesis Example 1, 3.00 g of a specific alkoxysilane-modified silica particle-containing solution (Si-1) and 0.46 g of GBL were added, followed by stirring at room temperature for 3 days. Then, it filtered through a 0.45 micron propylene filter, and the target varnish (organic-inorganic hybrid resin composition) was obtained. The obtained varnish was applied on the peeling layer with a bar coater (with a gap of 250 microns), and heated at 100°C for 1 hour using a hot plate. In a nitrogen atmosphere with a vacuum gas replacement furnace KDF-900GL (manufactured by Denken), the heating temperature was raised to 350°C (10°C/min), and heated again at 350°C for 30 minutes to obtain a transparent PI film L3. L3 could be easily peeled from the peeling layer as shown in FIG. 1. Table 1 shows the optical and thermal properties of L3.

Comparative Example 1

To 10 g of a 7 wt% polyimide GBL solution (PI-B) obtained in Synthesis Example 1, 4.66 g of a solution containing alkoxysilane-modified silica particles (Si-3) and 3.27 g of GBL were added, followed by stirring at room temperature for 3 days. Then, it filtered through a 0.45 micron propylene filter, and the target varnish was obtained. The obtained varnish was applied on the peeling layer with a bar coater (with a gap of 250 microns), and heated at 100°C for 1 hour using a hot plate. However, the varnish shrunk during heat drying, and a film could not be obtained.

Comparative Example 2

To 10 g of a 7 wt% polyimide GBL solution (PI-B) obtained in Synthesis Example 1, 4.66 g of a solution containing silica particles (Si-4) and 3.27 g of GBL were added, followed by stirring at room temperature for 3 days. Then, it filtered through a 0.45 micron propylene filter, and the target varnish was obtained. The obtained varnish was coated on an alkali-free glass substrate with a bar coater (with a gap of 250 microns), and heated at 100° C. for 1 hour using a hot plate. Again, it was heated on a hot plate at 280° C. for 30 minutes to obtain a transparent PI film HL2. Peeling was attempted on this film as in Fig. 1, but no peeling occurred, and cracks were generated.

Comparative Example 3

To 10 g of a 7 wt% polyimide GBL solution (PI-B) obtained in Synthesis Example 1, 4.66 g of a solution containing silica particles (Si-4) and 3.27 g of GBL were added, followed by stirring at room temperature for 3 days. Then, it filtered through a 0.45 micron propylene filter, and the target varnish was obtained. The obtained varnish was applied on a release layer plate with a bar coater (a gap of 250 microns), and heated at 100°C for 1 hour using a hot plate. Again, it was heated on a hot plate at 280° C. for 30 minutes to obtain a transparent PI film HL3. Peeling was attempted on this film as in Fig. 1, but no peeling occurred, and cracks were generated.

Comparative Example 4

10 g of a 7 wt% polyimide GBL solution (PI-B) obtained in Synthesis Example 1 was coated on a release layer plate with a bar coater (with a gap of 500 microns), and heated at 100° C. for 1 hour using a hot plate. Again, it was heated on a hot plate at 280° C. for 30 minutes to obtain a transparent PI film HL4. HL4 was able to be peeled off from the peeling layer as shown in FIG. 1. Table 1 shows the optical and thermal properties of HL4.

[Table 1]

As shown in Table 1, the films L1 to L3 obtained in the examples were easily peeled from the peeling layer to exhibit self-supporting properties, and exhibited excellent optical properties and low CTE. On the other hand, in Comparative Examples 1 to 3, a self-supporting film could not be obtained. In addition, in Comparative Example 4 in which the self-supporting film was obtained, it exhibited a high retardation value, had a lower light transmittance compared to the Example, and had a higher yellowness indicated by the CIE b ^* value, and showed a higher CTE than the Example. It was the result.

Claims (12)

An organic-inorganic hybrid resin composition comprising the following (A) component, (B) component and (C) component.
(A) component: inorganic fine particles having an average particle diameter of 1 nm to 100 nm, modified with an alkoxysilane compound having two aromatic groups having 6 to 18 carbon atoms or one aromatic group having 7 to 18 carbon atoms,
(B) component: polyimide having fluorine,
(C) Component: Organic solvent. The method of claim 1,
The organic-inorganic hybrid resin composition, wherein the alkoxysilane compound in the component (A) is a compound represented by the following formula (S1).
[Formula 1]

(In the formula,
R ¹ and R ² are each independently an alkyl group having 1 to 3 carbon atoms,
W is an integer from 1 to 3,
Y is an integer of 0-2, and W+Y=3,
Z ¹ represents a group selected from the group consisting of a halogen atom, an alkyl group having 1 to 10 carbon atoms, and an alkoxy group having 1 to 10 carbon atoms, m represents an integer of 0 to 5, provided that when m is an integer of 2 or more, Z ¹ May be the same or different groups.) The method according to claim 1 or 2,
In the above formula, m is 0, the organic-inorganic hybrid resin composition. The method according to any one of claims 1 to 3,
The polyimide of the component (B) is an imidized product of polyamic acid, which is a reaction product of a tetracarboxylic acid dianhydride component and a diamine component containing a fluorinated aromatic diamine represented by the following formula (A1). Hybrid resin composition.
[Formula 2]

(In the formula, B ² represents a divalent group selected from the group consisting of formulas (Y-1) to (Y-34).)
[Formula 3]

[Formula 4]

[Formula 5]

[Formula 6]

[Formula 7]

(In the formula, * represents the number of bonds.) The method of claim 4,
The organic-inorganic hybrid resin composition, wherein the tetracarboxylic dianhydride component contains an alicyclic tetracarboxylic dianhydride represented by the following formula (C1).
[Formula 8]

[In the formula, B ¹ represents a tetravalent group selected from the group consisting of formulas (X-1) to (X-12).
[Formula 9]

(In the formula, a plurality of R represents a hydrogen atom or a methyl group independently of each other, and * represents the number of bonds.) The method according to any one of claims 1 to 5,
The organic-inorganic hybrid resin composition, wherein the inorganic fine particles of the component (A) are silicon dioxide particles. The method according to any one of claims 1 to 6,
The organic-inorganic hybrid resin composition, wherein the mass ratio of the component (A) and the component (B) is 5:5 to 9::1 in terms of (A):(B). The method according to any one of claims 1 to 7,
The organic-inorganic hybrid resin composition, wherein the inorganic fine particles of the component (A) are inorganic fine particles having an average particle diameter of 1 nm to 60 nm. The method according to any one of claims 1 to 8,
The organic-inorganic hybrid resin composition, wherein the component (C) is an ester solvent. A resin thin film formed from the organic-inorganic hybrid resin composition according to any one of claims 1 to 9, which is transparent with a light transmittance of 80% or more at 400 nm and has a haze of 2% or less. A substrate for a flexible device comprising the resin thin film according to claim 10. As a method of manufacturing a substrate for a flexible device,
a) forming a release layer on the support substrate;
b) forming a resin thin film to be a substrate for a flexible device comprising the organic-inorganic hybrid resin composition according to any one of claims 1 to 9 on this release layer; And
c) removing the resin thin film from the peeling layer to obtain a flexible device substrate;
Including, the method.

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