TWI804564B - Hybrid resin composition - Google Patents

Abstract

The object of the present invention is to provide a resin composition that maintains excellent performance in heat resistance, low retardation, excellent flexibility, and excellent transparency, and at the same time provides a self-supporting substrate or a resin formed on it. A plastic film with excellent performance as the bottom film of flexible device substrates such as flexible display substrates that can be easily peeled off. The present invention is an organic-inorganic hybrid resin composition, which is an organic-inorganic hybrid resin composition comprising the following (A) component, (B) component and (C) component, (A) Component: The average particle size of the surface of the microparticles is modified with an alkoxysilane compound having 2 aromatic groups with 6 to 18 carbon atoms, or an alkoxysilane compound with 1 aromatic group with 7 to 18 carbon atoms Inorganic particles with a diameter of 1nm to 100nm, (B) component: polyimide which has fluorine, (C) Component: an organic solvent.

Description

mixed resin composition

The present invention relates to a mixed resin composition, and more specifically, the present invention relates to a film that can be peeled off by a mechanical peeling method from a peeling layer formed on a carrier substrate, and is suitable for forming a flexible display Composition of flexible device substrates.

In recent years, with the rapid progress of the electronics industry (Electronics) such as liquid crystal displays and organic electroluminescent displays, devices are required to be thinner, lighter, and more flexible. These devices form various electronic components on a glass substrate, such as thin film transistors or transparent electrodes, but by replacing the glass material with a soft and lightweight resin material, it is possible to expect thinning or lightening of the device itself. Quantification and flexibility. As a candidate for such a resin material, for example, polyimide has attracted attention, and there are various reports on polyimide films.

For example, Patent Document 1 reports the invention of polyimide and its precursors that can be used as plastic substrates for flexible displays. Tetracarboxylic acids containing alicyclic structures such as cyclohexylphenyl tetracarboxylic acid and Polyimides reacted with various diamines are excellent in transparency and heat resistance.

In addition, in Patent Document 2, by adding silicon sol to polyimide, the shortcomings of conventional plastic substrates are improved, that is, it has linear expansion coefficient, transparency, and low birefringence at the same time, and it can be fully expected to be applied to flexible substrates. Plastic substrates for displays.

While pursuing the advantages of the plastic substrate, the operability or dimensional stability of the plastic substrate itself becomes a problem. In other words, when the plastic substrate is formed into a thin film and thinned, wrinkles or cracks are likely to occur, and it is difficult to guarantee its own support. In addition, the positional accuracy of the thin film transistor (TFT) or functional layer formation of electrodes or the formation of functional layers Afterwards, it becomes difficult to maintain dimensional accuracy. Therefore, Non-Patent Document 1 proposes a method of forcibly separating the plastic substrate with the organic functional layer from the glass after forming a predetermined functional layer on the plastic substrate coated on the glass and adhering to it, and then irradiating laser light from the glass side. This is a so-called laser lift-off step (EPLaR method (Electronics on Plastic by Laser Release) method). [Prior Art Literature] [Patent Document]

[Patent Document 1] Japanese Patent Laid-Open No. 2008-231327 [Patent Document 2] International Publication No. 2015/152178 [Non-patent literature]

[Non-Patent Document 1] E.I. Haskal et. al. "Flexible OLED Displays Made with the EPLaR Process", Proc.Eurodisplay '07, pp.36-39 (2007)

[Problem to be Solved by the Invention]

The technique described in the above-mentioned Non-Patent Document 1 uses glass as a supporting substrate, and forms a functional layer by fixing it on a plastic substrate made of glass to ensure operability or 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. The problem of damage to the functional layer (TFT, etc.), or the problem of large damage to the resin substrate itself, the problem of lower transmittance, etc., may degrade the properties of the resin substrate and the functional layer formed on it.

The present invention is completed in view of the above circumstances. The purpose of the present invention is to provide a composition that does not rely on the above-mentioned laser lift-off technology, which provides a base film for flexible device substrates such as flexible display substrates ( base film) is a plastic film with excellent performance, especially maintaining excellent heat resistance, low retardation, excellent flexibility, and excellent transparency, and can ensure its handling or dimensional stability, and can be provided by A resin composition for a flexible device substrate that is mechanically peeled and peeled from a supporting base or a peeling layer, and a flexible device substrate obtained therefrom. [Means to solve the problem]

As a result of careful examination by the present inventors in order to achieve the above object, it was found that a resin composition in which a silica sol modified with a specific siloxane is blended with a heat-resistant polymer that can have both heat resistance and optical properties, The present invention has been accomplished by maintaining the characteristics of excellent heat resistance, low retardation, excellent flexibility, and excellent transparency, and being able to form a film that can be easily peeled off from a supporting substrate or the like.

(式中，R¹ 與R² 各自獨立為碳原子數1~3之烷基， W為1~3之整數， Y為0~2之整數，且W+Y=3， Z¹ 表示選自由鹵素原子、碳原子數1~10之烷基及碳原子數1~10之烷氧基所成群之基，m表示0至5之整數，但m為2以上之整數時，Z¹ 可為相同或相異的基)。 第3觀點：如第1觀點或第2觀點之有機無機混合樹脂組成物，其中前述式中，m為0。 第4觀點：如第1觀點至第3觀點中任一項之有機無機混合樹脂組成物，其中前述(B)成分之聚醯亞胺為四羧酸二酐成分與包含下述式(A1)表示之含氟芳香族二胺之二胺成分之反應生成物的聚醯胺酸之醯亞胺化物，

(式中，B² 表示選自由式(Y-1)~(Y-34)所成群之2價基)

(式中，*表示鍵結鍵)。 第5觀點：如第4觀點之有機無機混合樹脂組成物，其中前述四羧酸二酐成分包含下述式(C1)表示之脂環式四羧酸二酐，

[式中，B¹ 表示選自由式(X-1)~(X-12)所成群之4價基，

(式中，複數之R相互獨立表示氫原子或甲基，*表示鍵結鍵)]。 第6觀點：如第1觀點至第5觀點中任一項之有機無機混合樹脂組成物，其中前述(A)成分之無機微粒子為二氧化矽粒子。 第7觀點：如第1觀點至第6觀點中任一項之有機無機混合樹脂組成物，其中前述(A)成分與(B)成分之質量比(A)：(B)為5：5~9：1。 第8觀點：如第1觀點至第7觀點中任一項之有機無機混合樹脂組成物，其中前述(A)成分之無機微粒子為具有1nm至60nm之平均粒徑之無機微粒子。 第9觀點：如第1觀點至第8觀點中任一項之有機無機混合樹脂組成物，其中前述(C)成分為酯系溶劑。 第10觀點：一種樹脂薄膜，其係由如第1觀點至第9觀點中任一項之有機無機混合樹脂組成物所形成之400nm下之透光率(Luminous transmittance)80%以上，透明且具有2%以下之霧度。 第11觀點：一種可撓性裝置用基板，其係由第10觀點之樹脂薄膜而成。 第12觀點：一種可撓性裝置用基板之製造方法，其係包含以下步驟： a)在支撐基材上形成剝離層的步驟； b)在該剝離層上，形成由如第1觀點至第9觀點中任一項之有機無機混合樹脂組成物所成之成為可撓性裝置用基板之樹脂薄膜的步驟；及 c)將前述樹脂薄膜自剝離層剝離，得到可撓性裝置用基板的步驟。 [發明效果]That is, the first aspect of the present invention relates to an organic-inorganic hybrid resin composition comprising the following (A) component, (B) component, and (C) component. Ingredient: Inorganic with 2 aromatic groups with 6 to 18 carbon atoms or alkoxysilane compound with 1 aromatic group with 7 to 18 carbon atoms to modify the surface of fine particles with an average particle size of 1nm to 100nm Fine particles, (B) component: polyimide having fluorine, (C) component: organic solvent. The second aspect: the organic-inorganic hybrid resin composition according to the first aspect, wherein the alkoxysilane compound in the aforementioned component (A) is a compound represented by the following formula (S1),

(wherein, R ¹ and R ² are each independently an alkyl group with 1 to 3 carbon atoms, W is an integer of 1 to 3, Y is an integer of 0 to 2, and W+Y=3, Z ¹ represents a group selected from A halogen atom, an alkyl group with 1 to 10 carbon atoms, and an alkoxy group with 1 to 10 carbon atoms, m represents an integer from 0 to 5, but when m is an integer of 2 or more, ^Z1 can be the same or different bases). The third viewpoint: The organic-inorganic hybrid resin composition according to the first viewpoint or the second viewpoint, wherein m is 0 in the aforementioned formula. The fourth viewpoint: The organic-inorganic hybrid resin composition according to any one of the first viewpoint to the third viewpoint, wherein the polyimide of the aforementioned (B) component is a tetracarboxylic dianhydride component and contains the following formula (A1) The imide of polyamic acid, which is the reaction product of the diamine component of the fluorine-containing aromatic diamine,

(In the formula, ^B2 represents a divalent group selected from the group of formulas (Y-1)~(Y-34))

(In the formula, * represents a bonding bond). The fifth aspect: the organic-inorganic hybrid resin composition according to the fourth aspect, wherein the tetracarboxylic dianhydride component includes an alicyclic tetracarboxylic dianhydride represented by the following formula (C1),

[In the formula, B ¹ represents a quaternary group selected from formulas (X-1)~(X-12),

(In the formula, the plural Rs independently represent a hydrogen atom or a methyl group, and * represents a bonding bond)]. The 6th viewpoint: The organic-inorganic hybrid resin composition according to any one of the 1st viewpoint to the 5th viewpoint, wherein the inorganic fine particles of the aforementioned (A) component are silica particles. The seventh viewpoint: The organic-inorganic hybrid resin composition according to any one of the first viewpoint to the sixth viewpoint, wherein the mass ratio of (A) component to (B) component (A):(B) is 5:5~ 9:1. The 8th viewpoint: The organic-inorganic hybrid resin composition according to any one of the 1st viewpoint to the 7th viewpoint, wherein the inorganic fine particles of the aforementioned (A) component are inorganic fine particles having an average particle diameter of 1 nm to 60 nm. A ninth viewpoint: The organic-inorganic hybrid resin composition according to any one of the first viewpoint to the eighth viewpoint, wherein the aforementioned component (C) is an ester-based solvent. The tenth viewpoint: a resin film, which is formed of the organic-inorganic hybrid resin composition according to any one of the first viewpoint to the ninth viewpoint, has a light transmittance (Luminous transmittance) of 80% or more at 400 nm, is transparent and has Haze below 2%. An eleventh viewpoint: A substrate for a flexible device, which is made of the resin film according to the tenth viewpoint. The 12th viewpoint: A method of manufacturing a substrate for a flexible device, which includes the following steps: a) The step of forming a peeling layer on the supporting base; b) Forming the steps from the first viewpoint to the first viewpoint on the peeling layer A step of forming a resin film of the organic-inorganic hybrid resin composition according to any one of the 9 viewpoints to form a resin film for a substrate for a flexible device; and c) a step of peeling the aforementioned resin film from the release layer to obtain a substrate for a flexible device . [Invention effect]

According to the organic-inorganic hybrid resin composition of one aspect of the present invention, a resin film having a low coefficient of linear expansion, excellent heat resistance, low retardation, and excellent flexibility can be formed, and in addition, it can be formed without impairing these properties. Easy-to-peel resin film from a self-supporting substrate. In addition, the resin film formed by the organic-inorganic hybrid resin composition of the present invention exhibits high heat resistance, low linear expansion coefficient, high transparency (high light transmittance, low yellowness), low retardation, Moreover, it is also excellent in flexibility, so it can be suitably used as a base film for flexible devices, especially flexible display substrates. The organic-inorganic hybrid resin composition of the present invention and the resin film formed by the composition can fully respond to the requirements of high flexibility, low coefficient of linear expansion, high transparency (high light transmittance, low Yellowness), low retardation and other characteristics of the substrate for flexible devices, especially the development of the field of substrates for flexible displays.

The present invention will be described in detail below. 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: organic Solvent, if necessary, contain crosslinking agent and other components.

[Component (A): Inorganic microparticles whose surface is modified with a specific alkoxysilane] The component (A) is an inorganic fine particle whose surface is modified with a specific alkoxysilane described later. The average particle diameter of the inorganic fine particles can be appropriately selected depending on the purpose and the like. Among them, the average particle size is preferably 1 nm to 100 nm, for example, more preferably 1 nm to 60 nm, or 9 nm to 60 nm, particularly preferably 9 nm to 45 nm, in order to obtain a more transparent film. In the present invention, the average particle diameter of the inorganic fine particles is the average particle diameter calculated from the specific surface area value measured by the nitrogen adsorption method using the inorganic fine particles.

Inorganic fine particles, especially in the present invention, silicon dioxide (silicon dioxide) particles can be suitably used, for example, colloidal silicon dioxide having the above average particle diameter, and silicon sol can be used as the colloidal silicon dioxide. The silica sol can be an aqueous silica sol produced by a known method using an aqueous sodium silicate solution as a raw material, and an organosilicon melt obtained by replacing the water in the dispersion medium of the aqueous silica sol with an organic solvent. In addition, it is also possible to use alkoxysilane such as methyl silicate or ethyl silicate in organic solvent such as alcohol, catalyst (for example, alkali catalyst such as ammonia, organic amine compound, sodium hydroxide, etc.) Silica sol obtained by hydrolyzing and condensing the silica sol in the presence of presence, or the organosilicon melt that replaces the silica sol with other organic solvents. Among them, the silicone melt adhesive in which the dispersion medium is an organic solvent is preferred in the present invention.

Examples of organic solvents in the above-mentioned organosilicon melts include lower alcohols such as methanol, ethanol, and isopropanol; straight alcohols such as N,N-dimethylformamide and N,N-dimethylacetamide; Chain amides; Cyclic amides such as N-methyl-2-pyrrolidone; Ethers such as γ-butyrolactone; Ethyl cellosolve, glycols such as ethylene glycol, acetonitrile, etc. Substitution of water in the dispersion medium of the aqueous silica sol or substitution of other intended organic solvents can be carried out by ordinary methods such as distillation and ultrafiltration. The viscosity of the above silicone melt is about 0.6mPa･s~100mPa･s at 20°C.

Examples of commercially available products of the above-mentioned organosilicon melt include, for example, the product name MA-ST-S (methanol-dispersed silica sol, manufactured by Nissan Chemical Industry Co., Ltd. (currently: Nissan Chemical Co., Ltd., the same below)), the product name MT-ST (methanol dispersed silica sol, manufactured by Nissan Chemical Industry Co., Ltd.), trade name MA-ST-UP (methanol dispersed silica sol, manufactured by Nissan Chemical Industry Co., Ltd.), trade name MA-ST-M (methanol dispersed Silica sol, manufactured by Nissan Chemical Industry Co., Ltd.), trade name MA-ST-L (methanol-dispersed silica sol, manufactured by Nissan Chemical Industry Co., Ltd.), trade name IPA-ST-S (isopropyl alcohol-dispersed silica sol, Nissan Chemical Industry Co., Ltd.), trade name IPA-ST (isopropyl alcohol-dispersed silica sol, Nissan Chemical Industry Co., Ltd.), trade name IPA-ST-UP (isopropyl alcohol-dispersed silica sol, Nissan Chemical Industry Co., Ltd. )), trade name IPA-ST-L (Isopropanol Dispersed Silica Sol, manufactured by Nissan Chemical Industry Co., Ltd.), trade name IPA-ST-ZL (Isopropyl Alcohol Dispersed Silica Sol, manufactured by Nissan Chemical Industry Co., Ltd. ), trade name NPC-ST-30 (n-propyl cellosolve disperse silica sol, manufactured by Nissan Chemical Industry Co., Ltd.), trade name PGM-ST (1-methoxy-2-propanol disperse silica sol, Nissan Chemical Industry Co., Ltd.), trade name DMAC-ST (dimethylacetamide dispersion silica sol, Nissan Chemical Industry Co., Ltd. manufacture), trade name XBA-ST (xylene・n-butanol mixed solvent dispersion Silica sol, manufactured by Nissan Chemical Industry Co., Ltd.), trade name EAC-ST (ethyl acetate dispersed silica sol, manufactured by Nissan Chemical Industry Co., Ltd.), trade name PMA-ST (propylene glycol monomethyl ether acetate dispersed silica sol , Nissan Chemical Industry Co., Ltd.), trade name MEK-ST (methyl ethyl ketone dispersion silica sol, Nissan Chemical Industry Co., Ltd. production), trade name MEK-ST-UP (methyl ethyl ketone dispersion silica sol , Nissan Chemical Industry Co., Ltd.), trade name MEK-ST-L (methyl ethyl ketone dispersion silica sol, Nissan Chemical Industry Co., Ltd. production) and trade name MIBK-ST (methyl isobutyl ketone dispersion silicon Colloidal sol, manufactured by Nissan Chemical Industry Co., Ltd.), PL-1-IPA (isopropyl alcohol-dispersed silica sol, manufactured by Fuso Chemical Industry Co., Ltd.), PL-1-TOL (toluene-dispersed silica sol, manufactured by Fuso Chemical Industry Co., Ltd.) Manufactured), PL-2L-PGME (Propylene Glycol Monomethyl Ether Dispersed Silica Sol, manufactured by Fuso Chemical Industry Co., Ltd.), PL-2L-MEK (Methyl Ethyl Ketone Dispersed Silica Sol, manufactured by Fuso Chemical Industry Co., Ltd.), PL-3-ME (methanol-dispersed silica sol, manufactured by Fuso Chemical Co., Ltd.), etc., but not limited thereto. In the present invention, silica, for example, the silica listed above as the silicone melt used as the above-mentioned products, may also be used in admixture of two or more.

式中，R¹ 與R² 各自獨立為碳原子數1~3之烷基， W為1~3之整數， Y為0~2之整數，且W+Y=3， Z¹ 表示選自由鹵素原子、碳原子數1~10之烷基及碳原子數1~10之烷氧基所成群之基，m表示0至5之整數，但m為2以上之整數時，Z¹ 可相同或相異之基。 其中，m為0(聯苯基未被取代)烷氧基矽烷為佳。[Specific alkoxysilane] In the present invention, the alkoxysilane compound (hereinafter referred to as specific alkoxysilane) for modifying inorganic microparticles is an alkoxysilane compound having two aromatic groups with 6 to 18 carbon atoms. A base silane compound, or an alkoxy silane compound having an aromatic group with 7 to 18 carbon atoms. Examples of the above-mentioned aromatic group having 6 to 18 carbon atoms include a phenyl group and an aromatic group having 7 to 18 carbon atoms described below. The aromatic group having 7 to 18 carbon atoms includes a group having 2 to 3 benzene rings, a group having 2 to 4 condensed benzene rings, and the like. Among them, an alkoxysilane having a structure represented by the following formula (S1) having a biphenyl group which is an aromatic group having 7 to 18 carbon atoms is preferable.

In the formula, R ¹ and R ² are each independently an alkyl group with 1 to 3 carbon atoms, W is an integer of 1 to 3, Y is an integer of 0 to 2, and W+Y=3, Z ¹ represents a group selected from halogen atom, an alkyl group with 1 to 10 carbon atoms and an alkoxy group with 1 to 10 carbon atoms, m represents an integer from 0 to 5, but when m is an integer of 2 or more, Z ^{and 1} can be the same or base of difference. Among them, m is 0 (biphenyl is not substituted) alkoxysilane is preferred.

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

Inorganic microparticles whose surface is modified with a specific alkoxysilane, for example, when using silica particles as the inorganic microparticles, can be prepared by bringing the specific alkoxysilane into contact with the silica particles. When a specific alkoxysilane is brought into contact with silica particles, for example, the silanol group or alkoxysilyl group in the specific alkoxysilane undergoes a condensation reaction with the hydroxyl group present on the surface of the silica particles to form Silica particles with specific alkoxysilane modified surface. Specifically, for example, by mixing a colloidal solution of silica particles and a previously prepared specific alkoxysilane solution, it is possible to prepare silica particles whose surface is modified with a specific alkoxysilane. The mixing of the colloidal solution and the specific alkoxysilane solution can be carried out at room temperature or while heating. From the viewpoint of reaction efficiency, it is preferable to perform mixing while heating. When mixing while heating, the heating temperature can be appropriately selected according to the solvent and the like. When the heating temperature is, for example, 60° C. or higher, it is preferably the reflux temperature of the solvent.

The mixing ratio of the specific alkoxysilane and the silica particles can be appropriately selected depending on the purpose and the like. For example, the mass ratio of silica particles to specific alkoxysilanes (silicon dioxide particles/specific alkoxysilanes) is preferably 70/30~99/1, more preferably 70/30~90/10, More preferably, it is 80/20~90/10. Here, the mass number of the silica particles is calculated from the composition formula of the silica particles in the form of SiO ₂ .

(式中，B² 表示選自由式(Y-1)~(Y-34)所成群之2價基。)

(式中，*表示鍵結鍵。)[(B) Component: Polyimide] In the present invention, the polyimide preferably used is a polyimide having fluorine, more specifically, a tetracarboxylic dianhydride component and a fluorine-containing aromatic Diamine The polyimide (imide) obtained by imidizing the polyamic acid (reaction product) obtained by reacting the diamine component of the diamine. Among them, the above-mentioned fluorine-containing aromatic diamine is preferably a diamine represented by the following formula (A1).

(In the formula, ^B2 represents a divalent group selected from the group of formulas (Y-1)~(Y-34).)

(In the formula, * represents a bonding bond.)

[式中，B¹ 表示選自由式(X-1)~(X-12)所成群之4價基。

(式中，複數之R相互獨立表示氫原子或甲基，*表示鍵結鍵。)]It is preferable to use an alicyclic tetracarboxylic dianhydride as the aforementioned tetracarboxylic dianhydride component from the viewpoint of transparency and solubility in a solvent. Among them, the aforementioned alicyclic tetracarboxylic dianhydride is preferably one containing tetracarboxylic dianhydride represented by the following formula (C1).

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

(In the formula, the plural Rs independently represent a hydrogen atom or a methyl group, and * represents a bond.)]

Among the tetracarboxylic dianhydrides represented by the above-mentioned formula (C1), ^B in the formula is preferably a compound represented by the formulas (X-1), (X-4), (X-6), and (X-7) . Furthermore, among the diamines represented by the above-mentioned (A1), it is preferable that ^B2 in the formula is a compound represented by the formulas (Y-12) and (Y-13). A preferred example is that the polyamic acid obtained by reacting the tetracarboxylic dianhydride represented by the above-mentioned formula (C1) with the diamine represented by the above-mentioned formula (A1) carries out imidization. The polyimide system includes the following formula ( 2) The monomer unit represented.

In order to obtain a resin film (substrate for flexible devices) having the characteristics of low linear expansion coefficient, low retardation, and high transparency, and excellent flexibility, which is the object of the present invention, the total molar amount relative to the tetracarboxylic dianhydride component Number, alicyclic tetracarboxylic dianhydride, for example, the tetracarboxylic dianhydride represented by the above-mentioned formula (C1) is preferably more than 90 mol%, more preferably more than 95 mol%, especially all (100 mol%) ) is the most preferred tetracarboxylic dianhydride represented by the above formula (C1). Also, similarly, in order to obtain a resin film (substrate for flexible devices) having the characteristics of low linear expansion coefficient, low retardation, and high transparency as described above, and excellent flexibility, with respect to the total molar number of the diamine component, The fluorine-containing aromatic diamine, such as the diamine represented by formula (A1), is preferably at least 90 mol%, more preferably at least 95 mol%. Moreover, the diamine represented by the said formula (A1) may be sufficient as the whole (100 mol%) of a diamine component.

As an example of a preferable aspect, the polyimide used in this invention contains the monomer unit represented by following formula (1).

The monomer unit represented by the above formula (1) is preferably represented by formula (1-1) or formula (1-2), more preferably represented by formula (1-1).

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 monomer units represented by formula (1) and monomer units represented by formula (2) at the same time.

The monomer unit represented by the above formula (2) is preferably represented by formula (2-1) or formula (2-2), more preferably represented by formula (2-1).

When the polyimide used in the present invention comprises the monomer unit represented by the above-mentioned formula (1) and the monomer unit represented by the formula (2), the mole ratio in the polyimide chain, the unit represented by the formula (1) Monomer unit: The monomer unit represented by formula (2) = 10:1~1:10 ratio is better, more preferably 8:2~2:8 ratio, and 6:4~4:6 ratio The ratio is better.

In the polyimide of the present invention, in addition to the monopoly group derived from the alicyclic tetracarboxylic dianhydride component containing the tetracarboxylic dianhydride represented by the formula (C1) and the diamine component containing the diamine represented by the formula (A1), The monomer unit, for example, may contain other monomer units other than the monomer units represented by the above-mentioned formula (1) and formula (2). The content ratio of these other monomer units can be set arbitrarily as long as the properties of the resin film formed from the organic-inorganic hybrid resin composition of the present invention are not impaired. The ratio is relative to the monomer unit derived from the alicyclic tetracarboxylic dianhydride component containing the tetracarboxylic dianhydride represented by the aforementioned formula (C1) and the diamine component containing the diamine represented by the formula (A1), For example, the monomer unit represented by formula (1) or the mole number of the monomer unit represented by formula (2), or the total mole number of the monomer unit represented by formula (1) and the monomer unit represented by formula (2) , preferably less than 20 mol%, more preferably less than 10 mol%, more preferably less than 5 mol%.

式(3)中，A表示4價有機基，較佳為表示以下述式(A-1)~(A-4)之任一表示的4價基。又，上述式(3)中，B表示2價有機基，較佳為表示以式(B-1)~(B-11)之任一表示之2價基。各式中，*表示鍵結鍵。又，式(3)中，A為表示以下述式(A-1)~(A-4)之任一表示之4價基時，B也可為前述式(Y-1)~(Y-34)之任一表示之2價基。或式(3)中，B為表示下述式(B-1)~(B-11)之任一表示之2價基時，A也可為前述式(X-1)~(X-12)之任一表示之4價基。Such other monomer units include, for example, monomer units having other polyimide structures represented by formula (3), but are not limited thereto.

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). Also, in the above formula (3), B represents a divalent organic group, preferably a divalent group represented by any one of formulas (B-1) to (B-11). In each formula, * represents a bonding bond. Also, in formula (3), when A represents a tetravalent group represented by any one of the following formulas (A-1) to (A-4), B can also be the aforementioned formula (Y-1) to (Y- 34) A divalent group represented by any one of them. Or in formula (3), when B is the divalent group that represents any one of following formula (B-1)～(B-11), A also can be aforementioned formula (X-1)～(X-12 ) any one of the 4-valent base.

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

In addition, in the polyimide used in the present invention, each monomer unit may be bonded in any order.

A preferred example, the polyimide having the monomer unit represented by the above-mentioned formula (1) can be obtained by making bicyclo[2,2,2]octane-2,3,5, 6-Tetracarboxylic dianhydride and a diamine represented by the following formula (4) as a diamine component are obtained by polymerizing polyamic acid in an organic solvent and imidizing it. Also, when the polyimide used in the present invention has a monomer unit represented by the above formula (2), the polyimide can be obtained by using 1,2,3,4-ring as a tetracarboxylic dianhydride component. Butanetetracarboxylic dianhydride and a diamine represented by the following formula (4) as a diamine component are obtained by imidizing polyamic acid obtained by polymerizing in an organic solvent. In addition, when the polyimide used in the present invention has a monomer unit represented by the above formula (2) in addition to the monomer unit represented by the above formula (1), it contains each unit represented by the formula (1) and the formula (2). The polyimide of the body unit can be obtained by making the above-mentioned tetracarboxylic dianhydride as the tetracarboxylic dianhydride component, and making 1,2,3,4-cyclobutane tetracarboxylic dianhydride, and the diamine The diamine represented by the following formula (4) as a component is obtained by imidizing polyamic acid obtained by polymerization in an organic solvent.

The diamine represented by the above formula (4) includes 2,2'-bis(trifluoromethyl)benzidine, 3,3'-bis(trifluoromethyl)benzidine, 2,3'-bis(trifluoromethyl)benzidine, Fluoromethyl)benzidine. Among them, as the diamine component, the resin film (substrate for flexible device) of the present invention has a lower linear expansion coefficient, and the transparency of the resin film (substrate for flexible device) is higher. From a viewpoint, it is preferable to use 2,2'-bis(trifluoromethyl)benzidine represented by the following formula (4-1) or 3,3'-bis(trifluoromethyl)benzidine represented by the following formula (4-2) Fluoromethyl)benzidine, especially 2,2'-bis(trifluoromethyl)benzidine is preferably used.

上述式(5)中之A及式(6)中之B係分別表示與前述式(3)中之A及B相同意義。In addition, the polyimide used in the present invention is composed of an alicyclic tetracarboxylic dianhydride component comprising tetracarboxylic dianhydride represented by formula (C1) and a diamine component comprising diamine represented by formula (A1). The derived monomer unit, such as the monomer unit represented by the above-mentioned formula (1) and the monomer unit represented by the formula (2), when having other monomer units represented by the above-mentioned formula (3), include the formula (1), The polyimide of each monomer unit represented by formula (2) and formula (3) can be represented by the above-mentioned two kinds of tetracarboxylic dianhydrides as tetracarboxylic dianhydride components, and the following formula (5): Tetracarboxylic dianhydride and the diamine represented by the above-mentioned formula (4) as the diamine component, and the diamine represented by the following formula (6), and the polyamic acid obtained by polymerizing in an organic solvent is imidized And get.

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

Specifically, the tetracarboxylic dianhydride represented by the formula (5) includes pyromellitic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3,3',4, 4'-benzophenone tetracarboxylic dianhydride, 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride, 3,3',4,4'-diphenylsulfone tetracarboxylic dianhydride anhydride, 4,4'-(hexafluoroisopropylidene)diphthalic dianhydride, 11,11-bis(trifluoromethyl)-1H-difluoro[3,4-b:3',4 '-i]xanthene-1,3,7,9-(11H-tetraketone), 6,6'-bis(trifluoromethyl)-[5,5'-diisobenzofuran]-1, 1',3,3'-tetraketone, 4,6,10,12-tetrafluorodifuro[3,4-b:3',4'-i]dibenzo[b,e][1,4 ]dioxin-1,3,7,9-tetraketone, 4,8-bis(trifluoromethoxy)benzo[1,2-c:4,5-c']difuran-1,3,5 ,7-tetraketone, and N,N'-[2,2'-bis(trifluoromethyl)biphenyl-4,4'-diyl]bis(1,3-dioxo-1,3- Aromatic tetracarboxylic acids such as dihydroisobenzoran-5-formamide); 1,2-dimethyl-1,2,3,4-cyclobutane tetracarboxylic dianhydride, 1,2, 3,4-Tetramethyl-1,2,3,4-cyclobutane tetracarboxylic dianhydride, 1,2,3,4-cyclopentane tetracarboxylic dianhydride, 1,2,3,4- Alicyclic tetracarboxylic dianhydrides such as cyclohexanetetracarboxylic dianhydride and 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic dianhydride; and 1,2 , Aliphatic tetracarboxylic dianhydride such as 3,4-butane tetracarboxylic dianhydride, but not limited to these. Among these, A in the formula (5) is preferably the tetracarboxylic dianhydride of any one of the aforementioned formulas (A-1) to (A-4) representing a tetravalent group, that is, 11,11- Bis(trifluoromethyl)-1H-difluoro[3,4-b:3',4'-i]xanthene-1,3,7,9-(11H-tetraketone), 6,6'- Bis(trifluoromethyl)-[5,5'-diisobenzofuran]-1,1',3,3'-tetraketone, 4,6,10,12-tetrafluorodifuran[3,4 -b: 3',4'-i]dibenzo[b,e][1,4]dioxin-1,3,7,9-tetraone, and 4,8-bis(trifluoromethoxy) Benzo[1,2-c:4,5-c']difuran-1,3,5,7-tetraone is a preferred compound.

Also, the diamine represented by the formula (6) includes, for example, 2-(trifluoromethyl)benzene-1,4-diamine, 5-(trifluoromethyl)benzene-1,3-diamine, 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, tetra (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)diphenylamine, 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-(tri Fluoromethyl)benzidine, 2,2'-dimethylbenzidine (m-benzidine), 3,3'-dimethylbenzidine (o-benzidine), 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'-diaminobenzidine, 4-aminophenyl- 4'-aminobenzoate, octafluorobenzidine, 2,2',5,5'-tetramethylbenzidine, 3,3',5,5'-tetramethylbenzidine, 2,2 ',5,5'-tetrakis(trifluoromethyl)benzidine, 3,3',5,5'-tetrakis(trifluoromethyl)benzidine, 2,2',5,5'-tetrachlorobiphenyl Aniline, 4,4'-bis(4-aminophenoxy)biphenyl, 4,4'-bis(3-aminophenoxy)biphenyl, 4,4'-{[3,3”- Bis(trifluoromethyl)-(1,1':3',1"-terphenyl)-4,4"-diyl]-bis(oxygen)}diphenylamine, 4,4'-{[( Perfluoropropane-2,2-diyl)bis(4,1-phenylene)]bis(oxy)}diphenylamine, and 1-(4-aminophenyl)-2,3-dihydro-1 , 3,3-trimethyl-1H-indene-5 (or 6) amine and other aromatic diamines; 4,4'-methylenebis(cyclohexylamine), 4,4'-methylenebis (3-methylcyclohexylamine), isophoronediamine, trans-1,4-cyclohexanediamine, cis-1,4-cyclohexanediamine, 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)bicyclo[2.2.1]heptane, (Aminomethyl)tricyclo[5.2.1.0]decane, 1,3-diaminoadamantane, 2,2-bis(4-aminocyclohexyl)propane, 2,2-bis(4-amine Cyclohexyl)hexafluoropropane, 1,3-propanediamine, 1,4-tetramethylenediamine, 1,5-pentamethylenediamine, 1,6-hexamethylenediamine, 1,7-heptanediamine Aliphatic diamines such as (Heptamethylene diamine), 1,8-octanediamine, and 1,9-nonanediamine, but are not limited to these. Among these, B in the formula (6) is preferably an aromatic diamine having a divalent group represented by any of the aforementioned formulas (B-1) to (B-11), that is, 2,2 '-bis(trifluoromethoxy)-(1,1'-biphenyl)-4,4'-diamine [alternative name: 2,2'-dimethoxybenzidine], 4,4 '-(perfluoropropane-2,2-diyl)diphenylamine, 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 [other name: octafluorobenzidine], 2,3,5,6-tetrafluorobenzene-1, 4-diamine, 4,4'-{[3,3"-bis(trifluoromethyl)-(1,1':3',1"-terphenyl)-4,4"-diyl] -bis(oxy)}diphenylamine, 4,4'-{[(perfluoropropane-2,2-diyl)bis(4,1-phenylene)]bis(oxygen)}diphenylamine, and 1- (4-Aminophenyl)-2,3-dihydro-1,3,3-trimethyl-1H-indene-5(or 6)amine is a preferred diamine.

＜Synthesis of Polyamic Acid＞ In a preferred aspect of the polyimide used in the present invention, as mentioned above, the tetracarboxylic dianhydride component comprising the alicyclic tetracarboxylic dianhydride represented by the above formula (C1) is combined with the tetracarboxylic dianhydride component comprising the above formula (A1) It is obtained by imidizing the polyamic acid obtained by reacting the diamine component of the fluorine-containing aromatic diamine. Specifically, for example, a preferred example, by making bicyclo[2.2.2]octane-2,3,5,6-tetracarboxylic dianhydride, sometimes 1,2,3,4-cyclobutanetetra Carboxylic dianhydride, preferably the tetracarboxylic dianhydride component formed by the tetracarboxylic dianhydride represented by the above formula (5), and the diamine represented by the above formula (4) and more preferably represented by the above formula (6 ) The diamine component represented by the diamine component is obtained by imidizing the polyamic acid obtained by polymerization in an organic solvent. The reaction of the above-mentioned two components to polyamic acid is relatively easy in an organic solvent, and it is preferable in terms of not generating by-products.

The input ratio (molar ratio) of the diamine component in the reaction between the tetracarboxylic dianhydride component and the diamine component can be considered polyamic acid and polyimide obtained by imidization The molecular weight and the like are suitably set, but relative to the diamine component 1, the tetracarboxylic dianhydride component is usually about 0.8 to 1.2, for example, about 0.9 to 1.1, preferably about 0.95 to 1.02. Similar to the usual polycondensation reaction, the closer the molar ratio is to 1.0, the greater the molecular weight of the polyamic acid produced.

The organic solvent used for the reaction between the tetracarboxylic dianhydride component and the diamine component is not particularly limited as long as it does not affect the reaction and dissolves the polyamic acid produced. Specific examples thereof are given below. Examples include m-cresol, 2-pyrrolidone, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-vinyl-2-pyrrolidone, N,N-dimethylformamide, N,N-Dimethylacetamide, 3-methoxy-N,N-dimethylpropylamide, 3-ethoxy-N,N-dimethylpropylamide, 3-propane Oxy-N,N-dimethylpropylamide, 3-isopropoxy-N,N-dimethylpropylamide, 3-butoxy-N,N-dimethylpropylamide Amine, 3-sec-butoxy-N,N-dimethylpropylamide, 3-tert-butoxy-N,N-dimethylpropylamide, γ-butyrolactone, N- Methylcaprolactam, Dimethylsulfoxide, Tetramethylurea, Pyridine, Dimethylsulfoxide, Hexamethylcarbamide, Isopropanol, Methoxymethylpentanol, Dipentene, Ethylpentyl Base 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, Ethyl Carbitol, 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 monoethylene Ester 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-methyl Oxybutyl acetate, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, amyl acetate, butyl butyric acid Esters, butyl ether, diisobutyl ketone, methylcyclohexene, dipropyl ether, dihexyl ether, dioxane, n-hexane, n-pentane, n-octane, diethyl ether, cyclohexanone , ethylene carbonate, propylene carbonate, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether acetate, methyl pyruvate, ethyl pyruvate, 3-methoxy Methyl propionate, isopropyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionate, 3-methoxypropionate, 3-methoxypropionate Propyl, butyl 3-methoxypropionate, diglyme, and 4-hydroxy-4-methyl-2-pentanone, etc., but not limited thereto. These can be used individually or in combination of 2 or more types. In addition, even a solvent that does not dissolve polyamic acid may be used in admixture with the above-mentioned solvents within the range in which the produced polyamic acid does not precipitate. Moreover, the moisture in the organic solvent hinders the polymerization reaction and further causes the hydrolysis of the produced polyamic acid, so it is preferable to use an organic solvent that can dehydrate and dry as much as possible.

The method for reacting the above-mentioned tetracarboxylic dianhydride component and diamine component in an organic solvent includes stirring a dispersion or solution in which the diamine component is dispersed or dissolved in an organic solvent, directly adding the tetracarboxylic dianhydride component or adding The method of dispersing or dissolving the tetracarboxylic acid component in an organic solvent, on the contrary, the method of adding the diamine component to the dispersion or solution of the tetracarboxylic dianhydride component dispersed or dissolved in the organic solvent, the tetracarboxylic acid The method etc. which alternately add a dianhydride component and a diamine compound component may be any of these methods. In addition, when the tetracarboxylic dianhydride component and/or the diamine component are composed of multiple compounds, they can be reacted in a pre-mixed state, or they can be reacted individually and sequentially, and further, the low molecular weight body of the individual reaction can be carried out. Mixed reaction, as a high molecular weight body.

The temperature at the time of synthesizing the above-mentioned polyamide acid can be appropriately set within the range from the melting point to the boiling point of the solvent used above, for example, any temperature can be selected from -20°C to 150°C, and it can be from -5°C to 150°C. °C, usually about 0 to 150°C, preferably about 0 to 140°C. The reaction time is dependent on the reaction temperature or the reactivity of the raw materials, so it cannot be fully specified, but it is usually about 1 to 100 hours. Again, the reaction can be carried out at any concentration, but when the concentration is too low, it is difficult to obtain a polymer with a high molecular weight; The total concentration in the reaction solution of the amine component is preferably from 1 to 50% by mass, more preferably from 5 to 40% by mass. The initial stage of the reaction is carried out at a high concentration, and an organic solvent may be added thereafter.

＜Imidation of Polyamic Acid＞ As a method for imidating polyamic acid, thermal imidization in which a solution of polyamic acid is directly heated, and catalytic imidation in which a catalyst is added to a solution of polyamic acid are exemplified. The temperature for thermal imidization of polyamic acid in the solution is 100°C~400°C, preferably 120°C~250°C, and the water generated by the imidization reaction is preferably discharged to the outside of the system. .

The chemical (catalyst) imidization of polyamic acid is in the solution of polyamic acid, adding alkaline catalyst and acid anhydride, under the temperature condition of -20~250℃, preferably 0~180℃, This is performed by stirring the system. The amount of alkaline catalyst is 0.5~30 mole times of the amide acid group of polyamic acid, preferably 1.5~20 mole times, and the amount of acid anhydride is 1~30 mole times of the amide acid group of polyamic acid. 50 molar times, preferably 2 to 30 molar times.

Alkaline catalyst can enumerate pyridine, triethylamine, trimethylamine, tributylamine, trioctylamine, and 1-ethylpiperidine etc., wherein pyridine, 1-ethylpiperidine have reaction It needs moderate alkalinity, so it is better. The imidization rate of catalyst 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 ring-closing rate (imidization rate) of the amide acid group does not have to be 100%, and can be adjusted arbitrarily according to the application or purpose. The best is more than 50%.

In the present invention, the above-mentioned imidized reaction solution can be directly used to prepare an organic-inorganic hybrid resin composition without the step of recovering the polymer described later. At this time, after filtering the reaction solution, the filtrate itself or the The diluted or concentrated filtrate can be used in organic-inorganic hybrid resin composition. When filtered in this way, the incorporation of impurities which cause deterioration of the heat resistance, flexibility, or linear expansion coefficient characteristics of the obtained organic-inorganic hybrid resin film can be reduced.

In addition, the polyimide used in the present invention is made of the organic-inorganic hybrid resin composition in consideration of the strength of the resin film (organic-inorganic hybrid resin film) obtained from the organic-inorganic hybrid resin composition, and the strength of the support substrate. For the workability of the resin film, the uniformity of the organic-inorganic hybrid resin film, etc., the weight average molecular weight (Mw) obtained by gel permeation chromatography (GPC) in terms of polystyrene is preferably 5,000 to 200,000.

＜Polymer recycling＞ The polymer component is recovered from the reaction solution of polyamic acid and polyimide, and when this is used for the preparation of polyimide and the preparation of organic-inorganic hybrid resin composition, the reaction solution is put into a weak solvent to make Just settle. Examples of weak solvents used for precipitation include methanol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene, isopropanol, water, and the like. The polymer deposited in a weak solvent and precipitated can be recovered by filtration and then dried under normal pressure or reduced pressure at normal temperature or by heating. In addition, when the polymer recovered by precipitation is redissolved in an organic solvent, and the operation of re-precipitation recovery is repeated 2 to 10 times, the impurities in the polymer can be reduced. In this case, the weak solvent is preferably three or more kinds of weak solvents, such as alcohols, ketones, and hydrocarbons, because the efficiency of purification can be further improved.

In the reprecipitation recovery step, the organic solvent for dissolving the resin component 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, Dimethylpyrrolidone, Tetramethylurea, Pyridine, Dimethylpyrrolidone, Hexamethylpyrrolidone, γ-Butyrolactone, 1,3-Dimethyl-imidazole Phenone, dipentene, ethyl amyl ketone, methyl nonyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl ketone, cyclohexanone, ethylene carbonate, propylene carbonate , Diethylene glycol dimethyl ether, 4-hydroxy-4-methyl-2-pentanone, etc. These solvents can be used in combination of two or more kinds.

[other inorganic fine particles] The organic-inorganic hybrid resin composition of the present invention may contain other inorganic fine particles than the above-mentioned inorganic fine particles, that is, other inorganic fine particles not modified with a specific alkoxysilane compound. At this time, the content of other inorganic fine particles not modified with a specific alkoxysilane compound is based on the total of the inorganic fine particles of component (A) in this case and other inorganic fine particles not modified with a specific alkoxysilane compound, which is 50% by mass %~0 mass%, preferably 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 here may be a compound composed only of hydrogen atoms, carbon atoms, and oxygen atoms, or a compound composed of only hydrogen atoms, carbon atoms, nitrogen atoms, and oxygen atoms, having two or more compounds selected from A cross-linking agent formed by a group of hydroxyl group, epoxy group, and alkoxy group with 1 to 5 carbon atoms, and a compound with a ring structure. By using such a crosslinking agent, it is possible to provide a resin film suitable for a substrate for flexible devices having excellent solvent resistance with good reproducibility, and to realize an organic-inorganic hybrid resin composition with further improved storage stability. Wherein, the total number of the hydroxyl group, the epoxy group and the alkoxyl group of carbon number 1～5 of one of the compounds in the crosslinking agent is preferably 3 from the viewpoint of realizing the solvent resistance of the obtained resin film with good reproducibility. As mentioned above, from the viewpoint of realizing the flexibility of the obtained resin film with good reproducibility, it is preferably 10 or less, more preferably 8 or less, and more preferably 6 or less.

Specific examples of the ring structure of the crosslinking agent include aryl rings such as benzene, nitrogen atom-containing aryl heterocycles such as pyridine, pyrazine, pyrimidine, pyridazine, and 1,3,5-triazine ( heteroaryl rings), cycloalkane rings of cyclopentane, cyclohexane, cycloheptane, etc., rings of piperidine, piperazine, hexahydropyrimidine, hexahydropyridazine, hexahydro-1,3,5-triazine, etc. amines etc.

The number of ring structures of one of the compounds in the crosslinking agent is not particularly limited as long as it is 1 or more, but it is preferably 1 or 2. In addition, when there are two or more ring structures, the ring structures may be condensed with each other, or alkane with 1 to 5 carbon atoms such as methylene, ethylidene, propylidene, propane-2,2-diyl, etc.- A linking group such as a digroup, and a ring structure are bonded to each other.

The molecular weight of the cross-linking agent has cross-linking ability and is not particularly limited when it is dissolved in the solvent used. Consider the solvent resistance of the obtained resin film, the solubility of the cross-linking agent itself to organic solvents, the ease of acquisition or the price, etc. , preferably about 100~500, more preferably about 150~400.

The cross-linking agent may further have groups derived from hydrogen atoms, carbon atoms, nitrogen atoms, and oxygen atoms, such as ketone groups and ester groups (bonds).

As a preferred example of the cross-linking agent, compounds represented by any one of the following formulas (K1) to (K5) can be cited, and one of the preferred aspects of formula (K4) can be represented by formula (K4-1) One of the preferable aspects of the compound of formula (K5) includes a compound represented by formula (5-1).

In the above formula, each A ¹ and A ² independently represent an alkane with 1 to 5 carbon atoms such as methylene, ethylene, propylene, propane-2,2-diyl, etc. Diradical, wherein, A ¹ is preferably methylene, ethylene, more preferably methylene, and A ² is preferably methylene, propane-2,2-diyl.

In the above formulas (K1)~(K5), each X independently represents a hydroxyl group, an epoxy group (oxa-cyclopropyl group), or a methoxy group, an ethoxy group, a 1-propoxy group, an isopropoxy group, C1-5 alkoxy groups such as 1-butoxy and t-butoxy. Among them, when considering the ease of obtaining the crosslinking agent, price, etc., X is preferably an epoxy group in formulas (K1) and (K5), and is preferably a carbon atom in formulas (K2) and (K3). The alkoxy group with the number 1 to 5 is preferably a hydroxyl group in the formula (K4).

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

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

The compounds represented by the above formulas (K1) to (K5) can be obtained by combining a skeleton compound such as an aryl compound, a heteroaryl compound, or a cyclic amine having the same ring structure as that of each of these compounds, and a ring structure. Oxyalkyl halide compounds, alkoxy halide compounds, etc., are obtained by reacting carbon-carbon coupling reaction or N-alkylation reaction, or hydrolyzing the alkoxy part of the resultant.

As a crosslinking agent, a commercially available product may be used, or one 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, Same as 385, same 370, same 373, same 380, same 1116, same 1130, same 1133, same 1141, same 1161, same 1168, same 3020, same 202, same 203, same 1156, same MB-94, same MB- 96. Same as MB-98, same 247-10, same 651, same 658, same 683, same 688, same 1158, same MB-14, same MI-12-I, same MI-97-IX, same U-65 , Same as UM-15, Same as U-80, Same as U-21-511, Same as U-21-510, Same as U-216-8, Same as U-227-8, Same as U-1050-10, Same as U-1052 -8. Same as U-1054, same as U-610, same as U-640, same as UB-24-BX, same as UB-26-BX, same as UB-90-BX, same as UB-25-BE, same as UB-30 -B, same U-662, same U-663, same U-1051, same UI-19-I, same UI-19-IE, same UI-21-E, same UI-27-EI, same U-38 -I, same as UI-20-E, same as 659, same as 1123, same as 1125, same as 5010, same as 1170, same as 1172, same as NF3041, same as NF2000, etc. , Same as HP, Same as L, Same as PAS, Same as VL, Same as UC (manufactured by Nissan Chemical Industry Co., Ltd.), TM-BIP-A (manufactured by Asahi Organic Materials Co., Ltd.), 1,3,4,6 -Tetrakis(methoxymethyl)glycoluril (hereinafter referred to as TMG) (manufactured by Tokyo Chemical Industry Co., Ltd.), 4,4'-methylenebis(N,N-diglycidylaniline) (Aldrich system), 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 (stock)), TG-G (Shikoku Chemical Industry (stock)), etc.

Preferred specific examples of the crosslinking agent are listed below, but are not limited thereto.

The compounding amount of the cross-linking agent is appropriately determined according to the type of the cross-linking agent, so it cannot be fully specified, but usually relative to the mass of the aforementioned polyimide, or relative to the total mass of the aforementioned polyimide and the aforementioned inorganic fine particles, From the viewpoint of ensuring the flexibility and suppression of weakening of the obtained resin film, it is at most 50% by mass, preferably at most 100% by mass, and from the viewpoint of securing the solvent resistance of the obtained resin film, it is at least 0.1% by mass , preferably 1% by mass or more.

[(C): Organic solvent] The organic-inorganic hybrid resin composition of the present invention also contains an organic solvent in addition to the aforementioned polyimide, inorganic microparticles whose surface is modified with a specific alkoxysilane, any other inorganic microparticles, and a crosslinking agent. The organic solvent is not particularly limited, and examples thereof include the same ones as the specific examples of the reaction solvent used in the preparation of the above-mentioned polyamic acid and polyimide. More specifically, N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazoline Ketone, N-ethyl-2-pyrrolidone, γ-butyrolactone, etc. Moreover, an organic solvent may be used individually by 1 type, and may use it in combination of 2 or more types. Among them, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, and γ-butyrolactone are preferable in consideration of obtaining a resin film with high flatness and good reproducibility.

[Organic-inorganic hybrid resin composition] The present invention includes (A) inorganic fine particles whose surface is modified with a specific alkoxysilane, (B) the aforementioned polyimide, and (C) an organic solvent, and other inorganic fine particles containing silicon dioxide if necessary, Organic-inorganic hybrid resin composition such as cross-linking agent. Here, the organic-inorganic hybrid resin composition of the present invention is uniform and no phase separation is confirmed. In the organic-inorganic hybrid resin composition of the present invention, the compounding ratio of (A) the surface-modified inorganic microparticles with a specific alkoxysilane to (B) the aforementioned polyimide, in terms of mass ratio, (A) the inorganic microparticles : (B) Polyimide=10:1~1:10 is preferable, 8:2~2:8 is more preferable, for example, it can be 7:3~3:7, or 5:5~9:1. Also, when other inorganic fine particles not modified with a specific alkoxysilane compound are included, the above mass ratio may consider that the mass of (A) inorganic fine particles includes other inorganic fine particles. The content of other inorganic fine particles modified by compounds is based on the total of inorganic fine particles of component (A) in this case and other inorganic fine particles not modified with specific alkoxysilane compounds, and is 50% by mass to 0% by mass, preferably 20% by mass to 0% by mass. Also, the solid content in the organic-inorganic hybrid resin composition of the present invention is usually in the range of 0.5 to 30% by mass, but it is preferably at least 5% by mass and at most 20% by mass from the viewpoint of film uniformity. In addition, the solid content refers to the remaining components after removing the solvent from all the components constituting the organic-inorganic hybrid resin composition. In addition, the viscosity of the organic-inorganic hybrid resin composition is appropriately determined in consideration of the coating method used, the thickness of the resin film produced, etc., but it is usually 1~50,000mPa･s at 25°C.

In the organic-inorganic hybrid resin composition of the present invention, various organic or inorganic low-molecular or high-molecular compounds may be added in order to impart processability or various functionalities. For example, catalysts, defoamers, leveling agents, surfactants, dyes, plasticizers, fine particles, coupling agents, sensitizers, etc. can be used. For example, the catalyst can be added for the purpose of reducing the retardation or linear expansion coefficient of the resin film. The organic-inorganic hybrid resin composition of the present invention is the polyimide obtained by the above method, the above-mentioned inorganic microparticles whose surface is modified with a specific alkoxysilane compound, other inorganic microparticles such as desired silicon dioxide, and a crosslinking agent. It can be obtained by dissolving in the above-mentioned organic solvent, and the above-mentioned inorganic microparticles whose surface is modified with a specific alkoxysilane compound or its solution can also be added to the prepared reaction solution of polyimide, and silicon dioxide can be added as desired , cross-linking agent, etc., and the aforementioned organic solvent can also be added as desired.

[Resin films and substrates for flexible devices] The organic-inorganic hybrid resin composition of the present invention described above is coated on a substrate, and the organic solvent is removed by drying and heating, and can obtain excellent heat resistance, low retardation, excellent flexibility, and excellent transparency (high Light transmittance: for example, the light transmittance at 400nm is more than 80%, low yellowness: for example, the haze value is less than 2%) resin film, and can maintain these excellent properties, and at the same time through mechanical peeling A resin film that can be peeled from a release layer and can be used as a substrate for flexible devices. In addition, the resin film formed by the above-mentioned organic-inorganic hybrid resin composition, and the substrate for flexible devices, that is, the above-mentioned polyimide and the above-mentioned inorganic microparticles whose surface is modified with a specific alkoxysilane compound and desired A substrate for flexible devices containing inorganic microparticles such as silicon dioxide, a crosslinking agent, etc., that is, a substrate for flexible devices made of a cured product of the organic-inorganic hybrid resin composition of the present invention is also included in the present invention. object.

Substrates used in the production of substrates (resin films) for flexible devices include, for example, plastics (polycarbonate, polymethacrylate, polystyrene, polyester, polyolefin, epoxy, melamine, three Acetyl cellulose, ABS, AS, norcamphene-based resin, etc.), metal, stainless steel (SUS), wood, paper, glass, silicon wafer, slate, etc. Especially when used as a substrate for flexible devices, the existing equipment can be utilized. The base material used is preferably glass or silicon wafers, and the obtained substrate for flexible devices shows good peelability. Therefore, it is more preferably glass. The coefficient of linear expansion of the base material to be used is preferably 40 ppm/°C or less, more preferably 30 ppm/°C or less, from the viewpoint of warpage of the base material after coating.

When forming a peeling layer on a base material, a well-known method may be used. That is, after coating a known release layer-forming composition containing aromatic polyimide or polybenzoxazole on the substrate, it is fired at a temperature exceeding 450° C. by a known method, A release layer may be formed on the substrate. These can be used, for example, in International Publication No. 2017/204178, International Publication No. 2017/204182, International Publication No. 2017/204186, etc., as the composition for forming the release layer, the composition described in the release layer, and the release layer.

The coating method of the organic-inorganic hybrid resin composition on the base material or the release layer formed on the base material is not particularly limited, and examples thereof include cast coating, spin coating, knife coating, and dip coating method, roll coating method, rod coating method, die coating method, inkjet method, printing method (letterpanel, gravure, offset, screen printing, etc.), etc., and these coating methods can be used appropriately according to the purpose.

The heating temperature is preferably below 350°C. When it exceeds 350 degreeC, the obtained resin film becomes brittle, and the resin film suitable especially for display board|substrate use may not be obtained. In addition, when considering the heat resistance and linear expansion coefficient characteristics of the obtained resin film, the coated organic-inorganic hybrid resin composition is heated at 40°C to 100°C for 5 minutes to 2 hours, and in this state, it is gradually Raise the heating temperature, and finally, it is better to heat for 30 minutes to 2 hours at a temperature exceeding 175°C~350°C. In this way, the reproducibility is better and the low thermal expansion characteristic is exhibited by heating at two or more stages of the stage of drying the solvent and the stage of promoting molecular alignment. In particular, heat the coated organic-inorganic hybrid resin composition at 40°C~100°C for 5 minutes to 2 hours, then heat it at a temperature exceeding 100°C~175°C for 5 minutes~2 hours, and then heat it at a temperature exceeding 175°C~ It is better to heat for 5 minutes to 2 hours at 350°C. The utensils used for heating include, for example, a hot plate, an oven, and the like. The heating environment may be under air or under an inert gas such as nitrogen, under normal pressure or under reduced pressure, and different pressures may be used in each stage of heating.

The thickness of the resin film is within the range of about 1-200 μm, which can be appropriately determined by considering the type of flexible device, especially when it is assumed to be used as a substrate for a flexible display, it is usually about 1-60 μm, preferably About 5~50μm, adjust the thickness of the coating film before heating to form a resin film with the desired thickness. The method of peeling the resin film thus formed from the substrate is not particularly limited, and the resin film is cooled together with the substrate, and the film is cut and peeled, or a method of peeling by applying tension through a roller, and the like.

The resin film obtained in this way, which is a preferred aspect of the present invention, can achieve high transparency with a light transmittance of 80% or more at 400nm and a light transmittance of 90% or more at a wavelength of 550nm, preferably less than 2%. Low yellowness with a haze value below 1.5%. In addition, the resin film may have, for example, a coefficient of linear expansion in the range of 50°C to 200°C of 25 ppm/°C or less, particularly as low as 5 ppm/°C to 25 ppm/°C, and may have excellent dimensional stability during heating. In addition, this resin film has birefringence when the wavelength of incident light is set to 590 nm, that is, two birefringences when viewed from a cross-section in the thickness direction (the difference between the two refractive indices in the plane and the refractive index in the thickness direction) Respective difference) and the average value of the two phase differences obtained by multiplying the film thickness respectively are characterized by a small thickness retardation R _th .

The resin film described above has the above-mentioned characteristics, so those satisfying the various conditions necessary for the base film of flexible device substrates are particularly suitable for use as the base film of flexible devices, especially flexible display substrates.

In another aspect of the present application, a method for manufacturing a substrate for a flexible device is provided. This method can obtain a substrate for a flexible device by having the following steps. a) a step of forming a peeling layer on a supporting substrate such as a glass substrate; b) On the release layer, a step of forming a resin film to be a substrate for a flexible device using the organic-inorganic hybrid resin composition of the present invention; and c) A step of peeling the aforementioned resin film from the release layer to obtain a substrate for a flexible device. As shown in FIG. 1, the step c) above is a step of peeling off the resin film at the interface between the peeling layer (De-Bonding Layer) and the resin film (PI/silicon dioxide film) that becomes the substrate of the flexible device. The above-mentioned release layer can be formed by a known release-layer-forming composition containing the above-mentioned aromatic polyimide, polybenzoxazole, or the like. [Example]

The following examples are given to describe the present invention more specifically, 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: gamma-butyrolactone NMP: N-methyl-2-pyrrolidone

In addition, in the examples, the apparatus and conditions used for preparation of samples and analysis and evaluation of physical properties are as follows. 1) Measurement of number average molecular weight and weight average molecular weight Column: KD803 and KD805, column temperature: 50°C, dissolution solvent: DMF, flow rate: 1.0ml/min, calibration line: measured under the conditions of standard polystyrene. 2) Film thickness The film thickness of the obtained resin film was measured with a thickness gauge manufactured by Teclock Co., Ltd. 3) Coefficient of linear expansion (CTE) Using TMA Q400 manufactured by TA instruments, cut the film into a size with a width of 5mm and a length of 16mm. , cool down at 10°C/min, after cooling to 50°C, heat up at 10°C/min, when heating from 50°C to 420°C (second heating), measure the line from 50°C to 200°C during the second heating Obtained from the value of expansion coefficient (CTE [ppm/°C]). Also, a load of 0.05N was applied through the first heating, cooling and second heating. 4) Thermal decomposition temperature 5% weight loss temperature (Td _5% ) 5% weight loss temperature (Td _5% [°C]) is using TGA Q500 manufactured by TA Instruments Co., Ltd., making a film of about 5 to 10 mg in nitrogen gas, and 10 °C/min, obtained by measuring the temperature from 50 °C to 800 °C. 5) Light transmittance (transparency) (T _400nm , T _550nm ) and CIE b value (CIE b ^* ) Light transmittance (T _400nm , T _550nm [%]) and CIE b value ( CIE b ^* ) is measured by using an SA4000 spectrometer (Spectrometer) manufactured by Nippon Denshoku Industries Co., Ltd. at room temperature with air as a reference (reference). 6) Retardation (R _th ) Retardation in the thickness direction (R _th ) was measured at room temperature using KOBURA 2100ADH manufactured by Oji Scientific Instruments Co., Ltd. In addition, thickness direction retardation (R _th ) was calculated using the following formula. R _th =[(Nx+Ny)/2-Nz]×d=[(ΔNxz×d)+(ΔNyz×d)/2 Nx, Ny: In-plane orthogonal two refractive indices (Nx>Ny, Nx It is called the slow axis, and Ny is called the fast axis) Nz: relative to the surface, the refractive index in the thickness (perpendicular) direction 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) ADVANTEC is used for polyimide The Drv 320 vacuum oven manufactured by the company was used for drying.

在裝設有氮之注入口/排出口、機械攪拌器及冷卻器之250mL的反應三口燒瓶內中，加入TFMB 25.6g(0.08mol)。然後，添加GBL 173g，開始攪拌。二胺在溶劑中完全溶解後，隨即添加攪拌後的BODAxx 10.0g(0.04mol)、CBDA 7.84g(0.04mol)及GBL 43.4g，在氮氣下加熱至140℃。然後，將1-乙基哌啶0.35g添加於溶液內，氮氣下7小時加熱至180℃。最終停止加熱，將反應溶液稀釋至10%，整夜維持攪拌。將聚醯亞胺反應溶液添加於GBL：甲醇=50wt%：50wt%混合溶液2000g中，攪拌30分鐘後，藉由過濾聚醯亞胺固體，使聚醯亞胺純化。然後，該聚醯亞胺固體在甲醇2000g中攪拌30分鐘，過濾聚醯亞胺固體。此聚醯亞胺固體之攪拌及過濾之純化順序重複3次。藉由150℃下之真空烤箱之8小時乾燥，除去聚醯亞胺中之甲醇殘留物，最終得到乾燥後之21.5g之聚醯亞胺A。聚醯亞胺A(PI-A)之收率為51%(Mw=310,000、Mn=144,300)。將此PI-A7g置入500mL之三角燒瓶中，然後，加入GBL93g後，室溫下攪拌4日，得到7wt%之聚醯亞胺GBL溶液(PI-B)。[1] Synthesis example Synthesis example 1: Synthesis of polyimide A (PI-A) and preparation of 7wt% solution

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

Synthesis Example 2: Synthesis of varnish (DBL-1) for release layer 1.02 g (9.5 mmol) of p-PDA was dissolved in 26.4 g of NMP. 2.58 g (11.8 mmol) of PMDA was added to the obtained solution, and it was made to react at 23 degreeC under nitrogen atmosphere for 24 hours. Then, 0.44 g (4.7 mmol) of aniline was added, and it was made to react for 24 hours. The resulting polymer had a Mw of 31,500 and a molecular weight distribution of 3.2. 23 g of NMP was added to this solution, and it stirred at room temperature for 24 hours, and obtained the varnish (DBL-1) for peeling layers.

[2] Modulation example Preparation Example 1: Preparation of a solution containing silica particles modified with a specific alkoxysilane (Si-1) In a 500mL reaction three-neck flask equipped with a nitrogen inlet/discharge port and a cooler, add Quartron PL-1-IPA (manufactured by Fuso Chemical Industry Co., Ltd., registered trademark, particle size (specific surface area conversion) 10~ 15nm, dispersing medium isopropanol) 200g (13.3%) and, 4-biphenyltrimethoxysilane 1.644g. Then, under nitrogen atmosphere, it heated at 100 degreeC for 17 hours. After the reaction was completed, 79.8 g of GBL was added, and the isopropanol was distilled off under reduced pressure using an evaporator to obtain a GBL sol solution (Si-1) of silica particles modified with a specific alkoxysilane. Put 1 g of this solution on an aluminum cup, heat it at 200°C for 2 hours, calculate the concentration from the remaining amount, and the concentration is 35 wt%.

Preparation example 2: Preparation of a solution containing silica particles modified with a specific alkoxysilane (Si-2) In a 100mL reaction three-neck flask equipped with a nitrogen inlet/discharge port and a cooler, add Quartron PL-1-IPA (manufactured by Fuso Chemical Industry Co., Ltd., registered trademark, particle size (specific surface area conversion) 10~ 15nm, dispersing medium isopropanol) 50g (13.3%) and 4-biphenyltrimethoxysilane 0.206g. Then, under nitrogen atmosphere, it heated at 100 degreeC for 22 hours. After the reaction was completed, 19.9 g of GBL was added, and the isopropanol was distilled off under reduced pressure using an evaporator to obtain a GBL sol solution (Si-2) of silica particles modified with a specific alkoxysilane. Put 1 g of this solution on an aluminum cup, heat it at 200°C for 2 hours, calculate the concentration from the remaining amount, and the concentration is 35 wt%.

Preparation Example 3: Preparation of a solution containing silica particles modified with alkoxysilane (Si-3) In a 500mL reaction three-neck flask equipped with a nitrogen inlet/discharge port and a cooler, add Quartron PL-1-IPA (manufactured by Fuso Chemical Industry Co., Ltd., registered trademark, particle size (specific surface area conversion) 10~ 15nm, dispersing medium isopropanol) 200g (13.3%) and phenyltrimethoxysilane 1.13g. Then, under nitrogen atmosphere, it heated at 100 degreeC for 17 hours. After the reaction was completed, 79.8 g of GBL was added, and the isopropanol was distilled off under reduced pressure using an evaporator to obtain a GBL sol solution (Si-3) of silicon dioxide particles modified with alkoxysilane. Put 1 g of this solution on an aluminum cup, heat it at 200°C for 2 hours, calculate the concentration from the remaining amount, and the concentration is 35 wt%.

Preparation Example 4: Preparation of a solution containing silica particles (Si-4) In a 500mL eggplant-shaped flask, 200g (13.3%) of Quartron PL-1-IPA (manufactured by Fuso Chemical Industry Co., Ltd., registered trademark, particle size (specific surface area conversion) 10-15nm, dispersing medium isopropanol) and GBL79 .8g, using an evaporator to distill off isopropanol under reduced pressure to obtain a GBL sol solution (Si-4) of silicon dioxide particles not modified by alkoxysilane. Put 1 g of this solution on an aluminum cup, heat it at 200°C for 2 hours, calculate the concentration from the remaining amount, and the concentration is 35 wt%.

[3] Formation of peeling layer Using a spin coater (conditions: rotation speed 3,000rpm, about 30 seconds), apply the release layer varnish (DBL-1) obtained in Synthesis Example 2 on a 100mm x 100mm glass substrate as a glass substrate (the same applies below). superior. Then, heat the obtained coating film at 80°C for 10 minutes using a heating plate, then heat at 300°C for 30 minutes in an oven, raise the heating temperature (10°C/min) to 500°C, and then heat at 500°C for 10 minutes. A release layer with a thickness of about 0.1 μm was formed on the glass substrate. Also, during the heating period, the film-attached substrate was heated in the oven without being taken out from the oven.

[4] Preparation of composition and formation of thin film Example 1 To 10 g of the 7 wt % polyimide GBL solution (PI-B) obtained in Synthesis Example 1, 4.66 g of the solution (Si-1) containing silica particles modified with a specific alkoxysilane and 3.27 g of GBL were added, Stir at room temperature for 3 days. Then, it was filtered with a propylene filter of 0.45 microns to obtain the target varnish (organic-inorganic hybrid resin composition). The obtained varnish was coated on the release layer with a coating bar (gap: 250 μm), and heated at 100° C. for 1 hour using a heating plate. Then, it was heated on a heating plate at 280° C. for 30 minutes to obtain a transparent PI film L1. As shown in Fig. 1, the L1 series can be easily peeled from the peeling layer. The optical and thermal properties of L1 are shown in Table 1.

Example 2 A varnish (organic-inorganic hybrid resin composition) was obtained in the same manner as in Example 1, except that 4.66 g of the solution (Si-2) containing specific alkoxysilane-modified silica particles was used instead of the above (Si-1). . Coat the PI on the release layer to form a thin film to obtain a transparent PI film L2. Like L1, the L2 series can be easily peeled from the peeling layer. The optical and thermal properties of L2 are shown in Table 1.

Example 3 To 10 g of the 7wt% polyimide GBL solution (PI-B) obtained in Synthesis Example 1, 3.00 g of the solution (Si-1) containing silica particles modified with a specific alkoxysilane and 0.46 g of GBL were added, Stir at room temperature for 3 days. Then, it was filtered with a propylene filter of 0.45 microns to obtain the target varnish (organic-inorganic hybrid resin composition). The obtained varnish was coated on the release layer with a coating bar (gap: 250 μm), and heated at 100° C. for 1 hour using a heating plate. The vacuum gas substitution furnace KDF-900GL (manufactured by Denken) was used to raise the heating temperature (10°C/min) to 350°C under a nitrogen atmosphere, and then heated at 350°C for 30 minutes with a hot plate to obtain a transparent PI film L3. The L3 series can be easily peeled from the peeling layer as shown in FIG. 1 . The optical and thermal properties of L3 are shown in Table 1.

Comparative example 1 To 10 g of the 7 wt % polyimide GBL solution (PI-B) obtained in Synthesis Example 1, add 4.66 g of the solution (Si-3) containing silicon dioxide particles modified with alkoxysilane and 3.27 g of GBL, and Stir at room temperature for 3 days. Then, it was filtered through a 0.45-micron propylene filter to obtain the target varnish. The obtained varnish was coated on the release layer with a coating bar (gap: 250 μm), and heated at 100° C. for 1 hour using a heating plate. However, when heated and dried, the varnish shrinks and a thin film cannot be obtained.

Comparative example 2 To 10 g of the 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, and stirred at room temperature for 3 days. Then, it was filtered through a 0.45-micron propylene filter to obtain the target varnish. The obtained varnish was coated on an alkali-free glass substrate with a coating bar (gap: 250 μm), and heated at 100° C. for 1 hour using a heating plate. Then heated at 280° C. for 30 minutes on a heating plate to obtain a transparent PI film HL2. This film was peeled off in the same manner as in Fig. 1, but it could not be peeled off at all, and cracks occurred.

Comparative example 3 To 10 g of the 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, and stirred at room temperature for 3 days. Then, it was filtered through a 0.45-micron propylene filter to obtain the target varnish. The obtained varnish was coated on a peel-off laminate with a coating bar (gap: 250 μm), and heated at 100° C. for 1 hour using a heating plate. Then heated at 280° C. for 30 minutes on a heating plate to obtain a transparent PI film HL3. This film was peeled off in the same manner as in Fig. 1, but it could not be peeled off at all, and cracks occurred.

Comparative example 4 10 g of the 7 wt % polyimide GBL solution (PI-B) obtained in Synthesis Example 1 was coated on a peel-off laminate with a coating bar (gap 500 μm), and heated at 100° C. for 1 hour using a heating plate. Then heated at 280° C. for 30 minutes on a heating plate to obtain a transparent PI film HL4. The HL4 series can be peeled from the peeling layer as shown in Figure 1. The optical and thermal properties of HL4 are shown in Table 1.

As shown in Table 1, the films L1-L3 obtained in Examples can be easily peeled off from the release layer, exhibit self-supporting properties, exhibit excellent optical properties and low CTE. However, in Comparative Examples 1-3, self-supporting films could not be obtained. In addition, Comparative Example 4, which can obtain a self-supporting film, shows a high retardation value. Compared with the Examples, the light transmittance is lower, and the yellowness indicated by the CIE b ^* value is higher. In addition, compared with the Examples , showing higher CTE results.

[ Fig. 1 ] A schematic diagram of a method for peeling a substrate for a flexible device obtained from the organic-inorganic hybrid resin composition of the present invention from a supporting base material.

Claims (11)

An organic-inorganic hybrid resin composition, which is an organic-inorganic hybrid resin composition comprising the following (A) component, (B) component, and (C) component, (A) component: a compound represented by the following formula (S1) Inorganic microparticles with an average particle diameter of 1nm to 100nm on the surface of the microparticles, (B) component: polyimide with fluorine, (C) component: organic solvent,

(In the formula, R ¹ and R ² are each independently an alkyl group with 1 to 3 carbon atoms, W is an integer of 1 to 3, Y is an integer of 0 to 2, and W+Y=3, Z ¹ represents a group selected from A halogen atom, an alkyl group with 1 to 10 carbon atoms, and an alkoxy group with 1 to 10 carbon atoms, m represents an integer from 0 to 5, but when m is an integer of 2 or more, ^Z1 can be same or different basis). The organic-inorganic hybrid resin composition according to Claim 1, wherein in the aforementioned formula, m is 0. The organic-inorganic hybrid resin composition according to claim 1 or 2, wherein the polyimide of the aforementioned component (B) is a tetracarboxylic dianhydride component and a fluorine-containing aromatic diamine represented by the following formula (A1) The imide compound of polyamic acid, which is the reaction product of the amine component, H ₂ NB ² -NH ₂ (A1) (wherein, B ² is selected from formulas (Y-1)~(Y-34) group of divalent bases)

(In the formula, * represents a bonding bond). The organic-inorganic hybrid resin composition according to claim 3, wherein the aforementioned tetracarboxylic dianhydride component comprises alicyclic tetracarboxylic dianhydride represented by the following formula (C1),

[In the formula, B ¹ represents a quaternary group selected from formulas (X-1)~(X-12),

(In the formula, the plural Rs independently represent a hydrogen atom or a methyl group, and * represents a bonding bond)]. The organic-inorganic hybrid resin composition according to claim 1 or 2, wherein the inorganic fine particles of the aforementioned component (A) are silica particles. The organic-inorganic hybrid resin composition according to claim 1 or 2, wherein the mass ratio (A):(B) of the aforementioned component (A) to component (B) is 5:5~9:1. The organic-inorganic hybrid resin composition according to claim 1 or 2, wherein the inorganic fine particles of the aforementioned (A) component are inorganic fine particles having an average particle diameter of 1 nm to 60 nm. The organic-inorganic hybrid resin composition according to claim 1 or 2, wherein the aforementioned component (C) is an ester solvent. A resin film, which is formed by the organic-inorganic hybrid resin composition according to any one of claims 1 to 8, and has a light transmittance of 80% or more at 400nm Above, transparent and has a haze of 2% or less. A substrate for a flexible device, which is made of the resin film of claim 9. A method for manufacturing a substrate for a flexible device, comprising the following steps: a) forming a peeling layer on a support substrate; b) forming any one of claims 1 to 8 on the peeling layer A step of forming a resin film of the organic-inorganic hybrid resin composition into a substrate for a flexible device; and c) a step of peeling the aforementioned resin film from the release layer to obtain a substrate for a flexible device.

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