TWI735434B - Resin laminated film, laminated body containing it, TFT substrate, organic EL element, color filter and their manufacturing method. - Google Patents

Abstract

The subject of the present invention is to provide a resin laminated film that requires low irradiation energy for laser peeling using ultraviolet light.

The resin laminated film is a resin laminated film having a polyimide resin film on at least one surface of the resin film, and the polyimide resin film A is the following polyimide resin film.

Polyimide resin film A: When made into a film with a thickness of 100nm, in the wavelength range of 300~400nm, the minimum light transmittance is less than 50% of the polyimide resin film.

Description

Resin laminated films, laminated bodies containing them, TFT substrates, organic EL elements, color filters, and their manufacturing methods.

The present invention relates to a resin laminated film, a laminated body containing the same, a TFT substrate, an organic EL element, and methods for manufacturing them.

The resin film is more flexible than glass, is not easy to break, and is lighter. Recently, the use of resin film on the substrate of flat panel displays is being reviewed to make the display flexible.

唑、聚碳酸酯、聚醚碸、丙烯酸、環氧樹脂等。為了在顯示裝置或光學元件等的玻璃基板的替代材料中使用樹脂膜，要求耐熱性或在可見光區域的透明性等。作為顯示裝置，可舉出有機電致發光(有機EL)顯示器、液晶顯示器、電子紙等。作為光學元件，可舉出彩色濾光片，作為其它的構件，可舉出觸控面板。 Generally speaking, as the resin film, polyester, polyamide, polyimide, polyimide, polybenzo

Azole, polycarbonate, polyether stubble, acrylic, epoxy, etc. In order to use a resin film as a substitute material for a glass substrate such as a display device or an optical element, heat resistance, transparency in the visible light region, and the like are required. Examples of the display device include organic electroluminescence (organic EL) displays, liquid crystal displays, electronic paper, and the like. As an optical element, a color filter can be mentioned, and as another member, a touch panel can be mentioned.

As an example of a method of manufacturing a flexible substrate using a resin film, a step including a step of coating a resin varnish on a support substrate to form a resin film, a step of forming a display device or an optical element on the resin film, and the like The method of the step of peeling the resin film from the support substrate.

As a method of peeling a resin film from a supporting substrate, a laser peeling technique using ultraviolet light is disclosed (for example, refer to Patent Documents 1 and 2). In this method, by absorbing the heat generated by the laser light in the resin, the resin system near the interface with the supporting substrate is thermally decomposed, and the resin film is peeled from the supporting substrate.

[Prior Technical Literature] [Patent Literature]

Patent Document 1: Japanese Special Publication No. 2007-512568

Patent Document 2: Japanese Special Publication No. 2010-500609

However, heat-resistant resin films typified by polyimide have problems that the irradiation energy required for peeling is high and the laser peelability is poor.

It is believed that this is because the resin film has high heat resistance and is difficult to thermally decompose by laser irradiation. In addition, compared with colored polyimide, a transparent polyimide system with a high light transmittance in the visible light region requires higher irradiation energy for peeling. It is believed that this is due to heat resistance and low absorbance in the ultraviolet range.

Therefore, an object of the present invention is to provide a resin laminated film that requires a low irradiation energy for laser peeling using ultraviolet light in this wavelength range.

That is, the present invention is a resin laminated film, which is a resin laminated film having a polyimide resin film on at least one surface of the resin film, The aforementioned polyimide resin film is the following polyimide resin film A.

Polyimide resin film A: When making a film with a thickness of 100nm, in the wavelength range of 300~400nm, the minimum light transmittance is less than 50% of the polyimide resin film.

The resin laminated film system of the present invention can reduce the irradiation energy required for laser peeling of a self-supporting substrate.

1‧‧‧Support substrate

2. 2’‧‧‧Resin laminated film

2A, 2A’‧‧‧Polyimide resin film A

2B、2B’‧‧‧Resin film

3‧‧‧Black matrix

4R‧‧‧Red coloring pixel

4G‧‧‧Green coloring pixels

4B‧‧‧Blue coloring pixels

5‧‧‧Gas barrier

6‧‧‧TFT

7‧‧‧Planarization layer

8‧‧‧First electrode

9‧‧‧Insulation layer

10‧‧‧Second electrode

11R‧‧‧Red organic EL light-emitting layer

11G‧‧‧Green organic EL light-emitting layer

11B‧‧‧Blue organic EL light-emitting layer

11W‧‧‧White organic EL light-emitting layer

12‧‧‧Closed membrane

13‧‧‧Next layer

20‧‧‧CF

30‧‧‧Organic EL element

Fig. 1 is a cross-sectional view showing an example of a color filter substrate.

Fig. 2 is a cross-sectional view showing an example of a TFT substrate.

Fig. 3 is a cross-sectional view showing an example of an organic EL element display.

Fig. 4 is a cross-sectional view showing an example of an organic EL element display.

[The form of implementing the invention]

Hereinafter, the mode of carrying out the present invention will be described in detail. In addition, this invention is not limited by the following embodiment.

<Resin Laminated Film>

The resin laminated film of the present invention is a resin laminated film having a polyimide resin film on at least one surface of the resin film, and a polyimide resin film A below the aforementioned polyimide resin film.

Polyimide resin film A: When making a film with a thickness of 100nm, in the wavelength range of 300~400nm, the minimum light transmittance is less than 50% of the polyimide resin film.

Polyimide resin film A is preferably made in a thickness of 100nm When the film is at least one of the wavelengths of 308nm, 343nm, 351nm, and 355nm, the light transmittance is less than 50%.

Hereinafter, when a film with a thickness of 100nm is formed, in the wavelength range of 300~400nm, the minimum light transmittance is less than 50%, which is referred to as "physical properties (A)". In addition, when a film having a thickness of 100 nm is formed, the wavelength that gives the minimum light transmittance in the wavelength range of 300 to 400 nm is λ ₁ .

Since the polyimide resin film A satisfies the physical property (A), the laser light absorption of the wavelength near _{λ 1 is large.} Therefore, the heat generated by light absorption is large, and as a result, the irradiation energy required for laser peeling is lower than that of the polyimide resin film that does not satisfy the physical property (A). Hereinafter, the reduction in the irradiation energy required for laser peeling will be expressed as better laser peeling properties.

By reducing the irradiation energy required for laser peeling, the smoothness of the peeling surface of the resin film can be improved. For example, the lower the irradiation energy, the more the maximum height (Rz) of the peeling surface can be reduced. Since the smoothness of the peeling surface is increased, for example, the film-forming properties of the inorganic film on the peeling surface can be improved. If there are irregularities on the peeling surface, the coverage of the peeling surface by the inorganic film decreases, or pinhole defects occur in the inorganic film. These factors cause the decrease in the gas barrier properties of the inorganic film, etc., and are related to the decrease in the characteristics of the inorganic film. Therefore, the smoothness of the peeling surface is preferably high. In addition, the smoothness of the peeling surface can be evaluated with a surface roughness meter, AFM, or the like. In addition, as an index of smoothness, in addition to Rz, arithmetic average roughness (Ra), the maximum mountain height (Rp) of the roughness curve, the maximum valley depth (Rv) of the roughness curve, etc. may be used.

The polyimide system contained in the polyimide resin film A is not particularly limited, but it is preferably the main diamine residue in the polyimide resin film A. The component is derived from the following (B) diamine derivative.

(B) When making N-methyl-2-pyrrolidone solution with a concentration of 1×10 ^-4 mol/L, the maximum absorbance in the wavelength range of 300~400nm under the condition of the optical path length of 1cm It is a diamine derivative exceeding 0.6.

(B) The diamine derivative is more preferably in at least one of the wavelengths of 308nm, 343nm, 351nm, and 355nm when a N-methyl-2-pyrrolidone solution with ^{a concentration of 1×10 -4 mol/L is prepared,} A diamine derivative with an absorbance exceeding 0.6 under the condition of a light path length of 1 cm.

The diamine derivative includes a diamine compound obtained by reacting a diamine compound, a diisocyanate compound, and a silylating agent (an amide-based silylating agent, etc.).

In order for the polyimide resin film A to satisfy the physical properties (A), at least one of the acid dianhydride derivatives or diamine derivatives, which are the raw material monomers of the polyimide, must have an absorbance in the wavelength range of 300 to 400 nm Is high. Since the degree of freedom of molecular design of diamine derivatives is higher than that of acid dianhydride derivatives, it is easy to obtain diamine derivatives with high absorbance in the wavelength range of 300 to 400 nm.

Hereinafter, the polyimide having the diamine residue derived from the (B) diamine derivative as the main component is referred to as "polyimide B". The main component here means that the ratio of the diamine residues in all the diamine residues of the polyimide is higher than the total ratio of all the other diamine residues. In addition, the wavelength at which the (B) diamine derivative gives the maximum absorbance in the wavelength range of 300 to 400 nm is λ ₂ .

To polyimide B, in the vicinity of the wavelength [lambda] ₂ to give the minimum value of the light transmittance, the wavelength [lambda] ₂ of the vicinity of the laser light absorption becomes larger. Therefore, the heat generated by light absorption is large, and as a result, the irradiation energy system required for laser peeling becomes lower than that of polyimides other than polyimide B.

The manufacturing method of the resin laminated film of the present invention is not particularly limited, but it is preferable to perform a two-stage film manufacturing process as described later. As an example, first, a polyimide resin film A is produced on a supporting substrate such as a glass substrate as the first resin film (hereinafter referred to as "resin film 1"), and then a second resin film (hereinafter referred to as "resin film 1") is produced on the resin film 1. It is called "resin film 2"), the laser is irradiated from the glass substrate side, and the resin laminate film is peeled from the glass substrate. Since the resin film 1 exists on the glass substrate, regardless of the type of the resin film 2, the resin laminated film system exhibits good laser releasability.

The wavelength of laser irradiation is not particularly limited, and examples include 266 nm, 308 nm, 343 nm, 351 nm, and 355 nm. In addition, as long as the resin laminate film is peeled off, the light source is not limited to a laser, and a high-pressure mercury lamp, LED, etc. may also be used.

Such a resin laminated film preferably has a structure in which at least a resin film 1 and a resin film 2 are laminated in this order. In addition, the number of laminated layers of the resin film 2 is not particularly limited. The resin film 2 may be a single layer or a laminated film of two or more layers. For example, the resin film 2 may be the same as the resin film 1, including a polyimide resin. Resin layer. However, from the viewpoint of the transparency of the resin laminate film or the adhesion between layers, the number of laminate layers of the resin laminate film is preferably two. That is, the resin film 2 is preferably a single layer.

In addition, the resin laminated film of the present invention may also insert an inorganic film between the resin film 1 and the resin film 2. If an inorganic film is inserted, the gas barrier properties of the laminated film will increase, which is preferable.

The gas barrier layer on the resin film prevents water vapor, oxygen, etc. The task of penetration. Particularly in organic EL devices, the deterioration of the device due to moisture is significant, and therefore, the resin laminated film used as a substrate may be required to provide gas barrier properties.

Whether the resin film existing on the surface of the resin laminate film of the present invention satisfies physical property A can be measured by etching the resin laminate from the side opposite to the surface of the measurement object until the thickness becomes 100 nm. The light transmittance is confirmed.

As a specific method, for example, the following procedure can be used for measurement. First, the thickness of the resin laminate film is measured with a height difference meter, a scanning electron microscope (SEM), a micrometer, etc. At this time, by observing the fracture surface of the resin laminated film by SEM, the film thickness of each resin layer in the resin laminated film can also be measured. Then, fix the surface on the side of the measurement target to the glass substrate with adhesive tape, etc., and use methods such as glow discharge luminescence analyzer (GD-OES), reactive ion etching (RIE), gas cluster ion beam (GCIB), etc. Etching was performed from the surface of the resin laminate film on the opposite side of the measurement object to the surface of the measurement object side until the film thickness became 100 nm. The etching method is not particularly limited, but in terms of simultaneous element analysis of the resin film, GD-OES or GCIB is preferred. After etching until the film thickness reaches 100 nm, the light transmission spectrum is measured using a microscopy device. Perform the same etching and light transmittance measurement at 5 places, and set their average value as the light transmittance.

The resin composition of the resin laminate film of the present invention (for example, the molecular structure of the diamine residue of the resin film 1, etc.) or the film thickness of each layer can be determined by the total composition analysis using TPD-MS, TOF-SIMS or IR Spectrometry and precision oblique cutting method to analyze.

The minimum light transmittance of the polyimide resin film A is not particularly limited as long as it is less than 50%, but it is preferably less than 40%, more preferably less than 30%, and particularly preferably less than 20%. As the light transmittance becomes lower, the irradiation energy required for laser stripping decreases. When it is less than 20%, the effect of reducing the irradiation energy is particularly great.

(B) The maximum value of the aforementioned absorbance of the diamine derivative is not particularly limited as long as it exceeds 0.6, but it is preferably 0.8 or more, more preferably 1.0 or more. As the absorbance becomes higher, the irradiation energy required for laser stripping decreases. When it is 1.0 or more, the effect of reducing the irradiation energy is particularly great.

The thickness of the resin film 1 and the resin film 2 is not particularly limited, but from the viewpoints of transparency, heat resistance, and coefficient of linear thermal expansion (hereinafter also referred to as CTE) of the resin laminate film, the thickness of the resin film 1 is preferable It is 100nm~1μm, more preferably 100nm~0.5μm. When the thickness of the resin film 1 is 1 μm or less, the transparency of the resin film 1 in the visible light range becomes high. Therefore, the transparency of the resin laminate film in the visible light range is not impaired. In addition, the thickness of the resin film 1 is preferably thinner than the thickness of the resin film 2.

In addition, the ratio of the resin film 1 in the resin laminated film is not particularly limited, but the ratio of the resin film 1 is preferably 50% or less, more preferably 10% or less. By setting the ratio of the resin film 1 to 10% or less, it is possible to prevent the CTE of the entire resin laminate film from increasing. Specifically, the difference in CTE between the resin laminate film and the resin film 2 can be considerably reduced, for example, to 5 ppm/°C or less.

The CTE system of the resin laminated film of the present invention is not particularly defined, but it is preferably in the range of -10 to 30 ppm/°C in the range of 50°C to 200°C. Due to this range, the formation of resin on the support substrate can be reduced As a result of the warpage of the substrate during the build-up film, it is possible to fabricate TFT and other elements on the resin build-up film with high accuracy. In particular, when used as a TFT substrate, it is more preferably in the range of -10 to 20 ppm/°C, and still more preferably in the range of -10 to 10 ppm/°C.

The glass transition temperature (Tg) of the resin laminate film of the present invention is not specifically defined, but it is preferably 300°C or higher. In this range, the film forming temperature for the inorganic film on the resin laminate film can be increased, for example, the performance of the gas barrier layer or TFT can be improved. In particular, when forming a TFT, a temperature of 350°C or higher is generally used, so the Tg of the resin laminate film is more preferably 350°C or higher, and still more preferably 400°C or higher.

The transparency of the resin laminate film of the present invention is not specifically defined, but for substrates such as bottom emission organic EL displays, color filter substrates, touch panel substrates, etc., the substrate requires transparency in the visible light range. In this case, it is preferable that the resin laminated film is transparent.

The transparency mentioned here means that the transmitted light that is visually recognized through the resin laminate film has a color close to white. More specifically, it refers to the transmittance chromaticity of the resin laminate film in the XYZ colorimeter chromaticity diagram. The coordinates (x, y), for the chromaticity coordinates (x0, y0) of the light source, are (x-x0)/2+(y-y0)/2≦0.01.

Here, the so-called "transmission chromaticity coordinates" refers to the coordinates of the transmission chromaticity in the CIE1931 color system measured with a 2 degree field of view. As the kind of light source, for example, a C light source or the like can be given.

As a specific example that satisfies the aforementioned relational expression of (x-x0)/2+(y-y0)/2≦0.01, for example, the above-mentioned resin laminate film has a light transmittance of 80% at a wavelength of 400nm to 800nm. The above situation and so on. Furthermore, The transmittance chromaticity coordinates and light transmittance can be measured by forming the resin laminated film of the present invention on a glass substrate and using an ultraviolet-visible spectrophotometer or colorimeter.

(Resin film 1)

唑基]六氟丙烷、雙[2-(3-胺基苯基)-5-苯并

唑基]碸等。 The resin film 1 is not particularly limited as long as it is a polyimide resin film that satisfies the physical properties A. However, the polyimide component preferably contains polyimine B, and the polyimide component is more preferably because It is composed of polyimide B. (B) As long as the diamine derivative is ^{a N-methyl-2-pyrrolidone solution with a concentration of 1×10 -4} mol/L, it has an absorbance in the wavelength range of 300~400nm and a light path length of 1cm. Diamine derivatives whose maximum value exceeds a wavelength of 0.6 are not particularly limited. For example, bis[4-(4-aminophenoxy)phenyl]sulfonate, 9,9-bis(4-amine) Phenyl) pyrene, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, bis[4-(3-aminophenoxy)phenyl] chrysene, bis[ 3-(3-aminophenoxy)phenyl] chrysene, bis[3-(4-aminophenoxy)phenyl] chrysene, bis[4-(4-aminophenoxy)phenyl] Ether, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, bis(4-aminophenoxy)biphenyl, 2,2 -Bis[3-(3-aminobenzoamido)-4-hydroxyphenyl]hexafluoropropane, bis[3-(3-aminobenzoamido)-4-hydroxyphenyl]sulfonate , 2,2-bis[2-(3-aminophenyl)-5-benzo

Azolyl]hexafluoropropane, bis[2-(3-aminophenyl)-5-benzo

Azolyl] 碸 and so on.

In particular, it has high absorbance from 308nm light generally used as a light source for laser peeling, and it is preferable that the polyimide system of the resin film 1 has a main component derived from the formula (1) or (2). The diamine residue of the diamine derivative of the structure shown.

In the formulas (1)~(2), A represents a single bond, an oxygen atom, a sulfur atom, a sulfonyl group, a phenyl group, a stilbene group, a divalent organic group of 1 to 5 carbon atoms in which the hydrogen atom can be substituted by a halogen atom, Or a divalent organic group formed by connecting two or more of them. R ¹ to R ⁴ each independently represent a monovalent organic group having 1 to 10 carbon atoms having at least one amine group.

唑結構，此等結構係有效於提高在波長300~400nm之波長範圍的吸光度。 The formula (1) contains the hydroxyamide structure, and the formula (2) contains benzo

Azole structure, these structures are effective in increasing the absorbance in the wavelength range of 300~400nm.

唑結構的二胺殘基導入聚醯亞胺分子鏈中的第1方法，可舉出藉由具有式(1)所示的羥基醯胺結構之二胺化合物或其衍生物與酸二酐或其衍生物之反應所合成的聚醯亞胺前驅物之加熱閉環或化學的閉環反應，而使醯亞胺閉環與

唑閉環。作為第2方法，可舉出藉由具有式(2)所示的苯并

唑結構之二胺化合物或其衍生物與酸二酐或其衍生物之反應所合成的聚醯亞胺前驅物之加熱閉環或化學的閉環反應，而使醯亞胺閉環。 As will contain benzo

The first method of introducing the diamine residue of the azole structure into the polyimide molecular chain can be exemplified by using a diamine compound having a hydroxyamide structure represented by formula (1) or a derivative thereof with an acid dianhydride or The polyimine precursor synthesized by the reaction of its derivatives is heated or chemically closed to make the ring-closure of the imine and

Azole closed loop. As the second method, it can be exemplified by having a benzo

The polyimide precursor synthesized by the reaction of the diamine compound of the azole structure or its derivative and the acid dianhydride or its derivative is heated or chemically closed to close the ring of the imine.

唑閉環的加熱溫度係沒有特別的限定，但較佳為300℃以上，更佳為350℃以上。再者，藉由添加熱酸產生劑等的酸性觸媒，可降低

唑閉環的溫度。 The heating temperature for ring closure of the imine is not particularly limited, but is preferably 250°C or higher, more preferably 300°C or higher. Furthermore, by adding a basic catalyst such as imidazole, the ring closure temperature of the imine can be lowered. Used for

The heating temperature for azole ring closure is not particularly limited, but is preferably 300°C or higher, more preferably 350°C or higher. Furthermore, by adding acidic catalysts such as thermal acid generators, it is possible to reduce

The temperature at which the azole closes the ring.

唑結構，或式(1)、(2)的A為六氟亞異丙基。苯并

唑結構由於波長300-400nm的吸光度比羥基醯胺結構高，故有效於使雷射剝離所需要的照射能量降低。又，當A為六氟亞異丙基時，由於比單鍵、茀基、磺醯基等容易熱分解，故有效於使雷射剝離所需要的照射能量降低。 From the viewpoint of the laser releasability of the resin film 1, the diamine residue of the polyimide of the resin film 1 preferably contains the benzo

The azole structure, or A in formulas (1) and (2) is hexafluoroisopropylidene. Benzo

The azole structure has a higher absorbance at a wavelength of 300-400nm than the hydroxyamide structure, so it is effective in reducing the irradiation energy required for laser stripping. In addition, when A is a hexafluoroisopropylidene group, it is more easily thermally decomposed than a single bond, a stilbene group, a sulfonyl group, etc., so it is effective for reducing the irradiation energy required for laser stripping.

From the viewpoint of the transparency of the resin film 1 in the visible light range, A is preferably a hexafluoroisopropylidene group or a sulfonyl group. As the diamine derivative containing the structure represented by the general formula (1) or (2), for example, the polyimide, which is particularly preferably the resin film 1, has the following chemical formulas (3) to (6) in the main component: The diamine compound is derived from the diamine residue.

As the main component of the polyimide of the diamine residue-based resin film 1 derived from the diamine compounds represented by the general formulas (3) to (6), the transparency of the resin film 1 in the visible light range can be further improved . Therefore, without deteriorating the transparency of the resin laminate film, it can be applied to applications requiring transparency in the visible light range. Examples of such applications include substrates for bottom emission organic EL displays, color filter substrates, touch panel substrates, and the like.

Moreover, from the viewpoint of the heat resistance of the resin film 1, A is preferably a single bond or a phenyl group. Since A is a single bond or a phenyl group as the main component of the polyimide of the resin film 1, the heat resistance of the resin laminate film is further improved, so it can be used as a device that requires a high temperature process in the manufacturing process. Substrate. Specifically, it can be cited as the high temperature shape between the substrate and the element. The base material of organic EL display in the case of barrier layer, the base material of TFT which may be annealed at high temperature in order to ensure mobility or reliability.

When the polyimide of the resin film 1 contains diamine residues derived from the (B) diamine derivative as the main component, it may also contain diamine residues derived from other diamine derivatives. The main component here means that the ratio of the diamine residues in all the diamine residues of the polyimide is higher than the total ratio of all the other diamine residues.

It does not specifically limit as another diamine derivative, An aromatic diamine compound, an alicyclic diamine compound, or an aliphatic diamine compound is mentioned.

As the aromatic diamine compound, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenylmethane, 4 ,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane , 3,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide, 1,4-bis(4-aminophenoxy)benzene, benzidine, 2, 2'-bis(trifluoromethyl)benzidine, 3,3'-bis(trifluoromethyl)benzidine, 2,2'-dimethylbenzidine, 3,3'-dimethylbenzidine, 2,2',3,3'-Tetramethylbenzidine, 2,2'-Dichlorobenzidine, 3,3'-Dichlorobenzidine, 2,2',3,3'-Tetrachlorobenzidine , M-phenylenediamine, p-phenylenediamine, 1,5-naphthalenediamine, 2,6-naphthalenediamine, or the hydrogen atoms of these aromatic rings are replaced by alkyl, alkoxy, halogen atoms, etc. The diamine compound is not limited by these.

As the alicyclic diamine compound, cyclobutane diamine, isophorone diamine, bicyclo[2,2,1]heptane dimethylamine, tricyclo[3,3,1,13, 7] Decane-1,3-diamine, 1,2-cyclohexyldiamine, 1,3-cyclohexyl Diamine, 1,4-cyclohexyldiamine, trans-1,4-cyclohexyldiamine, cis-1,4-cyclohexyldiamine, 4,4'-diaminodicyclohexylmethane, 3, 3'-Dimethyl-4,4'-diaminodicyclohexylmethane, 3,3'-diethyl-4,4'-diaminodicyclohexylmethane, 3,3',5,5 '-Tetramethyl-4,4'-diaminodicyclohexylmethane, 3,3',5,5'-tetraethyl-4,4'-diaminodicyclohexylmethane, 3,5- Diethyl-3',5'-dimethyl-4,4'-diaminodicyclohexylmethane, 4,4'-diaminodicyclohexyl ether, 3,3'-dimethyl-4 ,4'-diaminodicyclohexyl ether, 3,3'-diethyl-4,4'-diaminodicyclohexyl ether, 3,3',5,5'-tetramethyl-4, 4'-diaminodicyclohexyl ether, 3,3',5,5'-tetraethyl-4,4'-diaminodicyclohexyl ether, 3,5-diethyl-3',5 '-Dimethyl-4,4'-diaminodicyclohexyl ether, 2,2-bis(4-aminocyclohexyl)propane, 2,2-bis(3-methyl-4-amino ring Hexyl) propane, 2,2-bis(3-ethyl-4-aminocyclohexyl)propane, 2,2-bis(3,5-dimethyl-4-aminocyclohexyl)propane, 2,2 -Bis(3,5-diethyl-4-aminocyclohexyl)propane, 2,2-(3,5-diethyl-3',5'-dimethyl-4,4'-diamine Dicyclohexyl) propane; or diamine compounds in which the hydrogen atoms of these alicyclic structures are replaced by alkyl groups, alkoxy groups, halogen atoms, etc., but are not limited by these.

Examples of the aliphatic diamine compound include ethylene diamine, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, and 1,6-diaminopropane. Alkyl diamines such as hexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, etc.; double (Aminomethyl)ether, bis(2-aminoethyl)ether, bis(3-aminopropyl)ether and other ethylene glycol diamines; and 1,3-bis(3-aminopropyl) Base) tetramethyldisiloxane, 1,3-bis(4-aminobutyl)tetramethyldisiloxane, α,ω-bis(3-aminopropyl)polydimethylsiloxane Siloxane diamines such as alkanes are not limited by these.

These aromatic diamine compounds, alicyclic diamine compounds, or aliphatic diamine compounds can be used alone or in combination of two or more kinds.

Known acid dianhydrides used in the production of polyimide in the resin film 1 can be used. The acid dianhydride is not particularly limited, and examples include aromatic acid dianhydrides, alicyclic acid dianhydrides, or aliphatic acid dianhydrides.

Examples of aromatic acid dianhydrides include pyromellitic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,3,3',4'-biphenyltetracarboxylic acid dianhydride Carboxylic dianhydride, 2,2',3,3'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-ditriphenyltetracarboxylic dianhydride, 3,3',4 ,4'-hydroxydiphthalic dianhydride, 2,3,3',4'-hydroxydiphthalic dianhydride, 2,3,2',3'-hydroxydiphthalic dianhydride, diphenyl Base-3,3',4,4'-tetracarboxylic dianhydride, diphenyl ketone-3,3',4,4'-tetracarboxylic dianhydride, 2,2-bis(3,4- Dicarboxyphenyl) propane dianhydride, 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, 1,1-bis(3,4-dicarboxyphenyl)ethane dianhydride, 1, 1-bis(2,3-dicarboxyphenyl)ethane dianhydride, bis(3,4-dicarboxyphenyl)methane dianhydride, bis(2,3-dicarboxyphenyl)methane dianhydride, 1, 4-(3,4-Dicarboxyphenoxy)phthalic anhydride, bis(1,3-dioxo-1,3-dihydroisobenzofuran-5-carboxylic acid) 1,4-phenylene -2,2-bis(4-(4-aminophenoxy)phenyl)propane, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic acid Dianhydride, 9,9-bis(3,4-dicarboxyphenyl) dianhydride, 2,3,5,6-pyridinetetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic acid two Anhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, 2,2-bis(4-(3,4-dicarboxybenzyloxy)phenyl)hexafluoropropane Dianhydride, 1,6-difluoropyromellitic dianhydride, 1-trifluoromethylpyromellitic dianhydride, 1,6-trifluoromethylpyromellitic dianhydride, 2,2'- Bis(trifluoromethyl)-4,4'-bis(3,4-dicarboxyphenoxy)biphenyl dianhydride, 2,2'-bis[(dicarboxyphenoxy)phenyl]propane Anhydride, 2,2'-bis[(dicarboxyphenoxy)phenyl] Hexafluoropropane dianhydride; or acid dianhydride compounds in which the hydrogen atoms of these aromatic rings are replaced by alkyl groups, alkoxy groups, halogen atoms, etc., but are not limited by these.

Examples of alicyclic dianhydrides include 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1S,2S,4R,5R-cyclohexanetetracarboxylic dianhydride, 1R,2S,4S ,5R-Cyclohexanetetracarboxylic dianhydride, etc. 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2 ,3,4-Tetramethyl-1,2,3,4-cyclobutane tetracarboxylic dianhydride, 1,2-dimethyl-1,2,3,4-cyclobutane tetracarboxylic dianhydride , 1,3-Dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 2,3,4,5-tetrahydrofurantetracarboxylic dianhydride, 3,4-dicarboxy-1- Cyclohexylsuccinic dianhydride, 2,3,5-tricarboxycyclopentylacetic dianhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalenesuccinic dianhydride, bicyclo[ 3,3,0]octane-2,4,6,8-tetracarboxylic dianhydride, bicyclo[4,3,0]nonane-2,4,7,9-tetracarboxylic dianhydride, bicyclo[ 4,4,0]decane-2,4,7,9-tetracarboxylic dianhydride, bicyclo[4,4,0]decane-2,4,8,10-tetracarboxylic dianhydride, tricyclic [6,3,0,0<2,6>]Undecane-3,5,9,11-tetracarboxylic dianhydride, bicyclo[2,2,2]octane-2,3,5,6 -Tetracarboxylic dianhydride, bicyclo[2,2,2]oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, bicyclo[2,2,1]heptanetetracarboxylic dianhydride , Bicyclo[2,2,1]heptane-5-carboxymethyl-2,3,6-tricarboxylic dianhydride, 7-oxabicyclo[2,2,1]heptane-2,4,6 ,8-tetracarboxylic dianhydride, octahydronaphthalene-1,2,6,7-tetracarboxylic dianhydride, tetradecanthracene-1,2,8,9-tetracarboxylic dianhydride, 3,3', 4,4'-Dicyclohexanetetracarboxylic dianhydride, 3,3',4,4'-hydroxydicyclohexanetetracarboxylic dianhydride, 5-(2,5-dioxotetrahydro-3 -Furyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic acid anhydride, "Rikacid" (registered trademark) TDA-100 (trade name, manufactured by Nippon Chemical Co., Ltd.) and their Derivatives; or hydrogen atoms of these alicyclic structures through alkyl, alkoxy, halogen atoms The acid dianhydride compound substituted by the zirconia is not limited by these.

Examples of aliphatic acid dianhydrides include 1,2,3,4-butanetetracarboxylic dianhydride, 1,2,3,4-pentanetetracarboxylic dianhydride, "Rikacid" (registered trademark) BT -100 (trade name, manufactured by Nippon Chemical Co., Ltd.), "Rikacid" (registered trademark) TMEG-100 (trade name, manufactured by Nippon Chemical Co., Ltd.), "Rikacid" (registered trademark) TMTA-C (product The name, New Japan Physical and Chemical (Stock) System), and their derivatives, etc. are not limited by these.

These aromatic acid dianhydrides, alicyclic acid dianhydrides, or aliphatic acid dianhydrides can be used alone or in combination of two or more kinds.

As the polyimide contained in the polyimide resin film A, from the viewpoint of improving the heat resistance, a polyimide having an aromatic acid dianhydride residue as a main component is preferred. In particular, if the aromatic acid dianhydride residue is derived from pyromellitic dianhydride or 3,3',4,4'-biphenyltetracarboxylic dianhydride, in addition to the improvement of heat resistance, The effect of lowering CTE can also be obtained, which is better.

In addition, as the polyimide contained in the polyimide resin film A, it is preferable to use an alicyclic acid from the viewpoint of transparency in the visible light range and reduction of the irradiation intensity required for laser peeling. Polyimide having a dianhydride residue as a main component, or an aliphatic acid dianhydride residue as a main component, or a total of alicyclic acid dianhydride residues and aliphatic acid dianhydride residues as a main component. In particular, as the polyimide B, it is preferable to have an alicyclic acid dianhydride residue as a main component, or an aliphatic acid dianhydride residue as a main component, or an alicyclic acid dianhydride residue and Polyimide whose main component is the total of aliphatic acid dianhydride residues. By having such acid dianhydride residues, the absorption of charge movement, which is one of the causes of the coloration of polyimide, is suppressed. Therefore, the transparency of the resin film 1 in the visible light range is improved. In addition, since these acid dianhydride residues are more easily thermally decomposed than aromatic acid dianhydride residues, the effect of reducing the irradiation intensity required for laser peeling becomes greater.

Furthermore, the so-called "contains aromatic acid dianhydride residues as the main component" means that the proportion of the aromatic acid dianhydride residues in the total acid dianhydride residues of the polyimide is higher than that of all other dianhydride residues. The total ratio of acid dianhydride residues is higher.

The so-called "contains alicyclic acid dianhydride residues as the main component" means that the proportion of the alicyclic acid dianhydride residues in the total acid dianhydride residues of polyimide is higher than that of all other acids. The total ratio of dianhydride residues is higher.

The so-called "aliphatic acid dianhydride residues as the main component" means that the proportion of the aliphatic acid dianhydride residues in the total acid dianhydride residues of polyimide is higher than that of all other acid dianhydrides The total ratio of residues is higher.

The so-called "the sum of the residues of the alicyclic acid dianhydride and the residues of the aliphatic acid dianhydride as the main component" refers to the alicyclic acid bis The total ratio of anhydride residues and aliphatic acid dianhydride residues is higher than the total ratio of all other acid dianhydride residues.

As long as these residues are the main component, the total ratio of acid dianhydrides is not limited, but from the viewpoint of laser releasability, it is preferably 75% or more.

Among alicyclic acid dianhydrides and aliphatic acid dianhydrides, from the viewpoint of ease of acquisition, cyclobutane tetracarboxylic dianhydride, 1S, 2S, 4R, 5R-cyclohexane tetra Carboxylic dianhydride, 1R, 2S, 4S, 5R-cyclohexane tetra Carboxylic dianhydride, 3,3',4,4'-dicyclohexanetetracarboxylic dianhydride, "Rikacid" (registered trademark) BT-100 (above, trade name, manufactured by Nippon Chemical Co., Ltd.), "Rikacid" (registered trademark) TMEG-100 (above, brand name, manufactured by Nippon Physicochemical Co., Ltd.), "Rikacid" (registered trademark) TMTA-C (above, brand name, manufactured by Nippon Physicochemical Co., Ltd.), "Rikacid" (registered trademark) TDA-100 (above, trade name, manufactured by Nippon Chemical Co., Ltd.).

Among these, from the viewpoint of reactivity with diamine derivatives, cyclobutane tetracarboxylic dianhydride represented by chemical formulas (7) to (10), 1S, 2S, 4R, 5R are more preferable -Cyclohexanetetracarboxylic dianhydride, 1R,2S,4S,5R-cyclohexanetetracarboxylic dianhydride, 3,3',4,4'-dicyclohexanetetracarboxylic dianhydride. That is, the alicyclic dianhydride residue in the polyimide is preferably derived from the tetracarboxylic dianhydride represented by any one of formulas (7) to (10).

Polyimide, and polyimide precursor resins such as polyimide acid, polyamidate, and polyamidate silylester, etc., in order to adjust the molecular weight to a better range, the end-blocking agent can be used to The two ends are closed. do The terminal blocking agent that reacts with acid dianhydride includes monoamines, monohydric alcohols, and the like. Moreover, as a terminal blocking agent which reacts with a diamine compound, an acid anhydride, a monocarboxylic acid, a monochlorine compound, a monoactive ester compound, a dicarbonate compound, a vinyl ether compound, etc. are mentioned. In addition, by reacting a terminal blocking agent, various organic groups can be introduced as terminal groups.

The monoamine used as the blocking agent for the acid anhydride group terminal includes 5-amino-8-hydroxyquinoline, 4-amino-8-hydroxyquinoline, 1-hydroxy-8-aminonaphthalene, 1-hydroxyl -7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 1-hydroxy-3-aminonaphthalene, 1-hydroxy -2-aminonaphthalene, 1-amino-7-hydroxynaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 2-hydroxy -4-aminonaphthalene, 2-hydroxy-3-aminonaphthalene, 1-amino-2-hydroxynaphthalene, 1-carboxy-8-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy -6-Aminonaphthalene, 1-carboxy-5-aminonaphthalene, 1-carboxy-4-aminonaphthalene, 1-carboxy-3-aminonaphthalene, 1-carboxy-2-aminonaphthalene, 1-amine 2-carboxy-7-carboxynaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-carboxy-4-aminonaphthalene, 2-carboxy -3-aminonaphthalene, 1-amino-2-carboxynaphthalene, 2-aminonicotinic acid, 4-aminonicotinic acid, 5-aminonicotinic acid, 6-aminonicotinic acid, 4 -Aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, cyanuric amide, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 2 -Aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4- Aminophenol, 5-amino-8-mercaptoquinoline, 4-amino-8-mercaptoquinoline, 1-mercapto-8-aminonaphthalene, 1-mercapto-7-aminonaphthalene, 1-mercapto- 6-aminonaphthalene, 1-mercapto-5-aminonaphthalene, 1-mercapto-4-aminonaphthalene, 1-mercapto-3-aminonaphthalene, 1-mercapto-2-aminonaphthalene, 1-aminonaphthalene -7-Mercaptonaphthalene, 2-Mercapto-7-aminonaphthalene, 2- Mercapto-6-aminonaphthalene, 2-mercapto-5-aminonaphthalene, 2-mercapto-4-aminonaphthalene, 2-mercapto-3-aminonaphthalene, 1-amino-2-mercaptonaphthalene, 3- Amino-4,6-dimercaptopyrimidine, 2-aminothiophenol, 3-aminothiophenol, 4-aminothiophenol, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 2,4-diethynylaniline, 2,5-diethynylaniline, 2,6-diethynylaniline, 3,4-diethynylaniline, 3,5-diethynylaniline, 1-ethynyl- 2-aminonaphthalene, 1-ethynyl-3-aminonaphthalene, 1-ethynyl-4-aminonaphthalene, 1-ethynyl-5-aminonaphthalene, 1-ethynyl-6-aminonaphthalene, 1-ethynyl-7-aminonaphthalene, 1-ethynyl-8-aminonaphthalene, 2-ethynyl-1-aminonaphthalene, 2-ethynyl-3-aminonaphthalene, 2-ethynyl-4 -Aminonaphthalene, 2-ethynyl-5-aminonaphthalene, 2-ethynyl-6-aminonaphthalene, 2-ethynyl-7-aminonaphthalene, 2-ethynyl-8-aminonaphthalene, 3 ,5-diethynyl-1-aminonaphthalene, 3,5-diethynyl-2-aminonaphthalene, 3,6-diethynyl-1-aminonaphthalene, 3,6-diethynyl-2 -Aminonaphthalene, 3,7-diethynyl-1-aminonaphthalene, 3,7-diethynyl-2-aminonaphthalene, 4,8-diethynyl-1-aminonaphthalene, 4,8 -Diethynyl-2-aminonaphthalene, etc., but not limited by these.

醇、萜品醇等，惟不受此等所限定。 Monohydric alcohols used as a blocking agent for the acid anhydride group terminal include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 1-pentanol, 2-pentanol, 3 -Pentanol, 1-hexanol, 2-hexanol, 3-hexanol, 1-heptanol, 2-heptanol, 3-heptanol, 1-octanol, 2-octanol, 3-octanol, 1 -Nonanol, 2-nonanol, 1-decanol, 2-decanol, 1-undecyl alcohol, 2-undecyl alcohol, 1-dodecanol, 2-dodecanol, 1-tridecanol, 2 -Tridecyl alcohol, 1-tetradecanol, 2-tetradecanol, 1-pentadecanol, 2-pentadecanol, 1-hexadecanol, 2-hexadecanol, 1-heptadecanol, 2-decenol Heptatanol, 1-octadecyl alcohol, 2-octadecyl alcohol, 1-nonadecanol, 2-nonadecanol, 1-eicosanol, 2-methyl-1-propanol, 2-methyl-2- Propanol, 2-methyl-1-butanol, 3-methyl-1-butanol, 2-methyl-2-butanol, 3-methyl-2-butanol, 2-propyl-1- Pentanol, 2-ethyl-1-hexanol, 4-methyl-3-heptanol, 6-methyl-2-heptanol, 2,4,4-trimethyl-1-hexanol, 2, 6-dimethyl-4-heptanol, isononanol, 3,7-dimethyl-3-octanol, 2,4-dimethyl-1-heptanol, 2-heptylundecanol, ethyl Glycol monoethyl ether, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, propylene glycol 1-methyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethyl Glycol monobutyl ether, cyclopentanol, cyclohexanol, cyclopentane monomethylol, dicyclopentane monomethylol, tricyclodecane monomethylol, drop

Alcohol, terpineol, etc., but not limited by these.

烯-2,3-二羧酸、1,2-二羧基萘、1,3-二羧基萘、1,4-二羧基萘、1,5-二羧基萘、1,6-二羧基萘、1,7-二羧基萘、1,8-二羧基萘、2,3-二羧基萘、2,6-二羧基萘、2,7-二羧基萘等之二羧酸類的僅1個羧基經醯氯化之單醯氯化合物；由單醯氯化合物與N-羥基苯并三唑或N-羥基-5-降

烯-2,3-二羧基醯亞胺之反應所得的活性酯化合物。 The acid anhydrides, monocarboxylic acids, monochlorine compounds, and monoactive ester compounds used as blocking agents for the amino terminal include phthalic anhydride, maleic anhydride, nadic acid anhydride, and cyclohexane. Acid anhydrides such as dicarboxylic anhydride and 3-hydroxyphthalic anhydride; 2-carboxyphenol, 3-carboxyphenol, 4-carboxyphenol, 2-carboxythiophenol, 3-carboxythiophenol, 4-carboxythiophenol, 1- Hydroxy-8-carboxynaphthalene, 1-hydroxy-7-carboxynaphthalene, 1-hydroxy-6-carboxynaphthalene, 1-hydroxy-5-carboxynaphthalene, 1-hydroxy-4-carboxynaphthalene, 1-hydroxy-3-carboxynaphthalene Naphthalene, 1-hydroxy-2-carboxynaphthalene, 1-mercapto-8-carboxynaphthalene, 1-mercapto-7-carboxynaphthalene, 1-mercapto-6-carboxynaphthalene, 1-mercapto-5-carboxynaphthalene, 1-mercapto -4-carboxynaphthalene, 1-mercapto-3-carboxynaphthalene, 1-mercapto-2-carboxynaphthalene, 2-carboxybenzenesulfonic acid, 3-carboxybenzenesulfonic acid, 4-carboxybenzenesulfonic acid, 2-ethynylbenzene Formic acid, 3-ethynyl benzoic acid, 4-ethynyl benzoic acid, 2,4-diethynyl benzoic acid, 2,5-diethynyl benzoic acid, 2,6-diethynyl benzoic acid, 3,4- Diethynyl benzoic acid, 3,5-diethynyl benzoic acid, 2-ethynyl-1-naphthoic acid, 3-ethynyl-1-naphthoic acid, 4-ethynyl-1-naphthoic acid, 5-ethynyl -1-naphthoic acid, 6-ethynyl-1-naphthoic acid, 7-ethynyl-1-naphthoic acid, 8-ethynyl-1-naphthoic acid, 2-ethynyl-2-naphthoic acid, 3-ethynyl -2-naphthoic acid, 4-ethynyl-2-naphthoic acid, 5-ethynyl-2-naphthoic acid, 6-ethynyl-2-naphthoic acid, 7-ethynyl-2-naphthoic acid, 8-ethynyl -2-Naphthoic acid and other monocarboxylic acids and these carboxyl chlorinated monochlorine compounds; and terephthalic acid, phthalic acid, maleic acid, cyclohexanedicarboxylic acid, 3-hydroxybenzene Dicarboxylic acid, 5-down

Ene-2,3-dicarboxylic acid, 1,2-dicarboxynaphthalene, 1,3-dicarboxynaphthalene, 1,4-dicarboxynaphthalene, 1,5-dicarboxynaphthalene, 1,6-dicarboxynaphthalene, 1,7-dicarboxynaphthalene, 1,8-dicarboxynaphthalene, 2,3-dicarboxynaphthalene, 2,6-dicarboxynaphthalene, 2,7-dicarboxynaphthalene and other dicarboxylic acids have only one carboxyl group Chlorinated mono-chlorine compounds; from mono-chlorine compounds and N-hydroxybenzotriazole or N-hydroxy-5-drop

An active ester compound obtained by the reaction of ene-2,3-dicarboxyimide.

The dicarbonate compound used as the blocking agent for the amino terminal includes di-tertiary butyl dicarbonate, diphenyl dicarbonate, dibenzyl dicarbonate, dimethyl dicarbonate, and diethyl dicarbonate.

Vinyl ether compounds used as a blocking agent for the amino terminal include tertiary butyl chloroformate, n-butyl chloroformate, isobutyl chloroformate, benzyl chloroformate, allyl chloroformate, ethyl chloroformate , Isopropyl chloroformate, methyl chloroformate, 2,2,2-trichloroethyl chloroformate and other chloroformates; butyl isocyanate, 1-naphthyl isocyanate, isocyanate Isocyanate compounds such as octadecyl ester and phenyl isocyanate; butyl vinyl ether, cyclohexyl vinyl ether, ethyl vinyl ether, 2-ethylhexyl vinyl ether, isobutyl vinyl ether, isopropyl vinyl ether, N-propyl vinyl ether, tertiary butyl vinyl ether, benzyl vinyl ether, etc.

Other compounds used as a blocking agent for the amine group include benzyl chloride, methanesulfonyl chloride, p-toluenesulfonyl chloride, isocyanide Phenyl acid ester and so on.

The introduction ratio of the blocking agent at the end of the acid anhydride group is preferably in the range of 0.1 to 60 mol%, and particularly preferably 1 to 50 mol%, relative to the acid dianhydride component. In addition, the introduction ratio of the blocking agent at the amino terminal is preferably in the range of 0.1 to 60 mol%, and particularly preferably 1 to 50 mol%, relative to the diamine component. In addition, by reacting a plurality of terminal blocking agents, a plurality of terminal groups can also be introduced.

The molecular structure of the repeating unit of the polyimide resin or the structure of the introduced end-blocking agent can be confirmed by the following method. For example, it can be easily detected by thermal decomposition gas chromatography (PGC) or infrared spectroscopy and ^{13 C NMR spectroscopy.} Furthermore, the polymer introduced with the end blocking agent is dissolved in an acidic solution to decompose into the amine component and acid anhydride component of the polymer's constituent units, and the measurement can be carried out by gas chromatography (GC) or NMR. Easily detect end blockers.

(Resin film 2)

唑樹脂、聚醯胺醯亞胺樹脂、聚醯胺樹脂、聚酯樹脂、聚碳酸酯樹脂、聚醚碸樹脂、丙烯酸樹脂、環氧樹脂等。其中，從耐熱性、機械特性等之觀點而言，較佳為含有選自包含聚醯亞胺樹脂、聚苯并

唑樹脂、聚醯胺醯亞胺樹脂及聚醯胺樹脂之群組中的至少1種的樹脂，再者從化學抗性或低CTE性之觀點而言，更佳為聚醯亞胺樹脂。 In the resin laminate film of the present invention, the type of resin of the resin film 2 is not particularly limited, and examples include polyimide resin, polybenzo

Azole resin, polyamide resin, polyamide resin, polyester resin, polycarbonate resin, polyether resin, acrylic resin, epoxy resin, etc. Among them, from the viewpoint of heat resistance, mechanical properties, etc., it is preferable to contain a resin selected from the group consisting of polyimide resin, polybenzo

At least one resin from the group of azole resin, polyimide resin, and polyimide resin, and from the viewpoint of chemical resistance or low CTE, polyimide resin is more preferable.

Known acid dianhydrides and diamines used in the synthesis of the polyimide resin in the resin film 2 can be used.

The acid dianhydride is not particularly limited, and examples include the aforementioned aromatic acid dianhydride, alicyclic acid dianhydride, or aliphatic acid dianhydride. These aromatic acid dianhydrides, alicyclic acid dianhydrides, or aliphatic acid dianhydrides can be used alone or in combination of two or more types. Moreover, it does not specifically limit as a diamine, For example, the above-mentioned aromatic diamine, alicyclic diamine, aliphatic diamine, etc. are mentioned. These aromatic diamines, alicyclic diamines, or aliphatic diamines can be used alone or in combination of two or more kinds. Furthermore, the aforementioned terminal blocking agent can also be used.

When polyimide resins are used for TFT substrates, base materials for top-emission organic EL displays, base materials for electronic paper, etc., heat resistance and low CTE are particularly required. At this time, the acid dianhydride used as the polyimide resin in the resin film 2 preferably contains pyromellitic dianhydride or 3,3',4,4'-biphenyltetracarboxylic dianhydride At least one type, as the diamine, it is preferable to include at least one type of 4,4'-diaminodiphenyl ether, p-phenylenediamine, and 3,3'-dimethylbenzidine.

On the other hand, when a polyimide resin is used in the base material of the bottom emission type organic EL display, the color filter base material, the touch panel base material, etc., heat resistance and high transparency in the visible light region are required. At this time, at least one of the acid dianhydride or diamine used in the polyimide resin in the resin film 2 preferably has an alicyclic structure or a fluorinated alkyl group. At this time, the polyimide resin of the resin film 2 has an alicyclic structure or a fluorinated alkyl group.

The alicyclic structure or the fluorinated alkyl group can be used for both or one of the acid dianhydride and the diamine. The diamine having an alicyclic structure is not particularly limited, but examples include trans-1,4-diaminocyclohexane and 4,4'-dicyclohexylmethane. As an acid dianhydride with an alicyclic structure , There is no particular limitation, but 1,2,3,4-cyclobutanetetracarboxylic dianhydride or 1R,2S,4S,5R-cyclohexanetetracarboxylic dianhydride and the like can be mentioned. The diamine having a fluorinated alkyl group is not particularly limited, but for example, 2,2'-bis(trifluoromethyl)benzidine can be mentioned. The acid dianhydride having a fluorinated alkyl group is not particularly limited, but 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride and the like can be mentioned.

In the polyimide resin film using these compounds, from the viewpoint of transparency and low CTE, the acid dianhydride preferably contains 3,3',4,4'-biphenyl tetrakis The carboxylic dianhydride preferably contains trans-1,4-diaminocyclohexane as the diamine.

(Manufacturing method of polyimide precursor)

Hereinafter, a general production method of the polyimide precursor will be explained. Generally speaking, the polyimide resin represented by the following general formula (11) is formed by making the polyimine precursor resin represented by the following general formula (12) undergo amide ring-closure (imidization). Response). The method of the imidization reaction is not particularly limited, and thermal imidization or chemical imidization can be mentioned. Among them, from the viewpoint of the heat resistance of the polyimide resin film and the transparency in the visible light region, thermal imidization is preferred.

In the general formulas (11) and (12), R ⁵ represents a tetravalent organic group, and R ⁶ represents a divalent organic group. X ¹ and X ² each independently represent a hydrogen atom, a monovalent organic group having 1 to 10 carbons, or a monovalent alkylsilyl group having 1 to 10 carbons.

Polyimine precursors such as polyamide acid, polyamide ester, polyamide silyl ester, etc. can be synthesized by the reaction of a diamine compound or its derivative with an acid dianhydride or its derivative. Examples of derivatives of acid dianhydride include tetracarboxylic acid, chlorinated acid, mono-, di-, tri-, or tetra-ester of the acid dianhydride, etc., specifically including methyl, ethyl , N-propyl, isopropyl, n-butyl, secondary butyl, tertiary butyl and other esterified structures. The reaction method of the polymerization reaction is not particularly limited as long as it can produce the desired polyimide precursor, and a well-known reaction method can be used.

As a specific reaction method, a specified amount of all the diamine components and the reaction solvent are added to the reactor and dissolved, and then the Add the specified amount of acid dianhydride and stir at room temperature to 120°C for 0.5 to 30 hours.

烷、丙二醇單甲基醚等之醚類；丙酮、甲基乙基酮、二異丁基酮、二丙酮醇等之酮類；醋酸乙酯、丙二醇單甲基醚乙酸酯、乳酸乙酯等之酯類；甲苯、二甲苯等之芳香族烴類等。 As the reaction solvent, N-methyl-2-pyrrolidone, γ-butyrolactone, N,N-dimethylformamide, and N,N-dimethylacetamide can be used alone or in two or more types. , N,N-dimethyl propylene urea, 1,3-dimethyl-2-imidazolidinone, dimethyl sulfide and other polar aprotic solvents; tetrahydrofuran, two

Ethers such as alkane and propylene glycol monomethyl ether; ketones such as acetone, methyl ethyl ketone, diisobutyl ketone, and diacetone alcohol; ethyl acetate, propylene glycol monomethyl ether acetate, ethyl lactate Esters such as toluene and xylene; aromatic hydrocarbons such as toluene and xylene.

The content of the solvent in the polyimide precursor resin composition, relative to 100 parts by weight of the polyimide precursor, is preferably 50 parts by weight or more, more preferably 100 parts by weight or more, and preferably 2,000 parts by weight Parts by weight or less, more preferably 1,500 parts by weight or less. If it is in the range of 50 to 2,000 parts by weight, the viscosity becomes suitable for coating, and the film thickness after coating can be easily adjusted.

(Manufacturing method of resin laminated film)

The resin laminated film of the present invention can be produced by a production method including at least the following steps (1) to (3).

(1) A step of manufacturing polyimide resin film A on a supporting substrate.

(2) A step of further laminating a resin film on the aforementioned resin film to form a resin laminated film.

(3) The step of irradiating ultraviolet light from the side of the supporting substrate to peel off the aforementioned resin laminate film.

The following describes the use of polyimide precursors and solvents The polyimide precursor solution, the resin film 1 and the resin film 2 are the manufacturing methods of the polyimide resin laminated film.

(1) Steps of manufacturing polyimide resin film A on the supporting substrate

The polyimide precursor resin solution is coated on the supporting substrate to form the polyimide precursor resin composition film of the polyimide resin film A. As the supporting substrate, for example, silicon, ceramics, gallium arsenide, soda lime glass, alkali-free glass, etc. are used, but they are not limited to these. The coating method includes, for example, a slit coating method, a spin coating method, a spray coating method, a roll coating method, a bar coating method, and the like, and it is also possible to apply a combination of these methods. Among these, coating by spin coating or slit coating is preferred.

Next, the polyimide precursor resin composition coated on the support substrate is dried to obtain a polyimide precursor resin composition film. The drying system uses hot plates, ovens, infrared rays, vacuum chambers, etc. When a hot plate is used, the support substrate coated with the polyimide precursor resin composition is held on the plate directly or on a fixture such as a proxy pin provided on the plate, and heated. As the material of the proximity needle, there are metal materials such as aluminum or stainless steel, or synthetic resin such as polyimide resin or "Teflon" (registered trademark). Any material of the proximity needle can be used. The height of the proximity needle varies depending on the size of the support substrate, the type of resin composition, the purpose of heating, etc., for example, a resin composition coated on a glass support substrate of 300mm×350mm×0.7mm When heating, the height of the proximity needle is preferably about 2-12 mm.

Among them, it is preferable to use a vacuum chamber for vacuum drying, and it is more preferable to perform heating for drying after the vacuum drying, or while vacuuming Heating for drying is performed while drying. Thereby, it is possible to shorten the drying process time and form a uniform coating film system. The heating temperature for drying varies depending on the type and purpose of the supporting substrate or the polyimide precursor, and is preferably in the range of room temperature to 170° C. for 1 minute to several hours. Furthermore, the drying step can be performed multiple times under the same conditions or under different conditions.

Next, heating for imidization is performed. The polyimide precursor resin composition film is heated in the range of 170° C. to 650° C. to be converted into a polyimide resin film. Furthermore, the thermal imidization step can also be carried out after the above-mentioned drying step and after any steps.

The gas environment of the thermal imidization step is not particularly limited, and it may be an inert gas such as air, nitrogen, or argon, or it may be in a vacuum. However, if firing is performed in an environment with a high oxygen concentration, the fired film will become brittle due to oxidative degradation, and the mechanical properties will be reduced. In order to suppress such a decrease in mechanical properties, it is preferable to calcinate in a gas atmosphere with an oxygen concentration of 5% or less. On the other hand, the management of oxygen concentration at the ppm level is often difficult at the manufacturing site. The resin film of the present invention is preferred because it can maintain higher mechanical properties as long as the oxygen concentration in the thermal imidization step is 5% or less. Furthermore, when colorless transparency is required, it is also preferable to perform thermal imidization by heating in an environment with an oxygen concentration of 5% or less. Generally speaking, by reducing the oxygen concentration, the coloration of the polyimide film in the thermal imidization step can be reduced, and a polyimide resin film showing high transparency can be obtained.

In addition, in the thermal imidization step, a heating method that conforms to the heating mode of the oven of the production line can be selected, but it preferably takes 5 to 300 minutes to raise the temperature to the maximum heating temperature. For example, you can put The polyimide precursor resin composition film formed on the substrate takes 5 to 300 minutes from room temperature to heat up to the highest heating temperature to undergo imidization to form a polyimide resin film; In an oven preheated to a range of 170°C or higher and 650°C or lower, the polyimide precursor resin film formed on the substrate is suddenly thrown in and heat-treated to perform imidization to form polyimide Amine resin film. In addition, the number of steps in the temperature increase process is not particularly limited, and the temperature may be increased in one step from the substrate input temperature to the maximum heating temperature, or may be increased in multiple steps with two or more steps.

(2) The step of further laminating a resin film on the aforementioned resin film to form a resin laminated film

Next, the second polyimide precursor resin solution was applied, and dried in the same manner as the first layer to produce a resin film 2 to form a resin laminated film.

In addition, from the viewpoint of increasing the glass transition temperature of the resin laminate film, it is preferable that the firing temperature of the resin film used in at least one of the steps (1) or (2) is 400° C. or higher.

(3) The step of irradiating ultraviolet light from the side of the supporting substrate to peel off the aforementioned resin laminate film

Ultraviolet light is irradiated from the supporting substrate side, and the resin laminate film is peeled from the supporting substrate. Since the resin film 1 is present on the support substrate, regardless of the type of the resin film 2, the resin laminated film system exhibits good laser releasability.

The wavelength system of the ultraviolet light is not particularly limited, and examples include 266 nm, 308 nm, 343 nm, 351 nm, and 355 nm. In addition, the light source is not particularly limited as long as the resin laminate film is peeled off by a laser, a high-pressure mercury lamp, an LED, or the like.

Furthermore, the polyimide precursor resin solution or polyimide resin film used in the film formation of resin films 1 and 2 may also contain surfactants, internal mold release agents, silane coupling agents, and thermal crosslinking Agents, inorganic particles, ultraviolet absorbers, photoacid generators, etc. In addition, these systems can be contained in the resin films 1 and 2 within a range that does not impair the required physical properties.

As the surfactant, Fluorad (trade name, manufactured by Sumitomo 3M Co., Ltd.), Megafac (trade name, manufactured by DIC Co., Ltd.), Sulfuron (trade name, manufactured by Asahi Glass Co., Ltd.), etc. can be mentioned. Agent. In addition, KP341 (trade name, manufactured by Shin-Etsu Chemical Co., Ltd.), DBE (trade name, manufactured by Chisso Co., Ltd.), Glanol (trade name, manufactured by Kyoeisha Chemical Co., Ltd.), BYK (BYK Chemical Co., Ltd.) (Stock) system) and other organosiloxane surfactants. In addition, polyoxyalkylene lauryl ether, polyoxyethylene lauryl ether, polyoxyethylene oleyl ether and polyoxyethylene cetyl ether, or Polyflow (manufactured by Sanyo Chemical Industry Co., Ltd.), etc., can be mentioned. Trade name, acrylic polymer surfactants of Kyoeisha Chemical Co., Ltd. etc.

The thermal crosslinking agent is preferably an epoxy compound or a compound having at least two alkoxymethyl groups or hydroxymethyl groups. Since it has at least two of these groups, it undergoes condensation reaction with the resin and the same molecules to form a cross-linked structure, which can improve the mechanical strength or chemical resistance of the cured film after heat treatment.

As preferred examples of epoxy compounds, for example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, polymethyl ( Epoxy-containing polysiloxanes such as glycidoxypropyl)silicone, etc., but the present invention is not limited by these at all. Specifically, Epiclon 850-S, Epiclon HP-4032, Epiclon HP-7200, Epiclon HP-820, Epiclon HP-4700, Epiclon EXA-4710, Epiclon HP-4770, Epiclon EXA-859CRP, Epiclon EXA-1514, Epiclon EXA-4880, Epiclon EXA-4850-150 , Epiclon EXA-4850-1000, Epiclon EXA-4816, EpiclonEXA-4822 (the above trade names, manufactured by Dainippon Ink Chemical Industry Co., Ltd.), Rikaresin BEO-60E, Rikaresin BPO-20E, Rikaresin HBE-100, Rikaresin DME- 100 (the above product names, manufactured by New Japan Physical and Chemical Co., Ltd.), EP-4003S, EP-4000S (the above product names, manufactured by ADEKA (share)), PG-100, CG-500, EG-200 (the above product names, Osaka Gas Chemical Co., Ltd.), NC-3000, NC-6000 (the above product names, manufactured by Nippon Kayaku Co., Ltd.), EPOX-MK R508, EPOX-MK R540, EPOX-MK R710, EPOX-MK R1710, VG3101L, VG3101M80 (trade names above, manufactured by PRINTEC Co., Ltd.), Celloxide 2021P, Celloxide 2081, Celloxide 2083, Celloxide 2085 (trade names above, manufactured by DAICEL Chemical Industry Co., Ltd.), etc.

Examples of compounds having at least two alkoxymethyl groups or hydroxymethyl groups include DML-PC, DML-PEP, DML-OC, DML-OEP, DML-34X, DML-PTBP, DML-PCHP, DML -OCHP, DML-PFP, DML-PSBP, DML-POP, DML-MBOC, DML-MBPC, DML-MTrisPC, DML-BisOC-Z, DML-BisOCHP-Z, DML-BPC, DML-BisOC-P, DMOM -PC, DMOM-PTBP, DMOM-MBPC, TriML-P, TriML-35XL, TML-HQ, TML-BP, TML-pp-BPF, TML-BPE, TML-BPA, TML-BPAF, TML-BPAP, TMOM -BP, TMOM-BPE, TMOM-BPA, TMOM-BPAF, TMOM-BPAP, HML-TPPHBA, HML-TPHAP, HMOM-TPPHBA, HMOM-TPHAP (above, trade name, Honshu Chemical Industry Co., Ltd.), NIKALAC (registered trademark) MX-290 , NIKALAC MX-280, NIKALAC MX-270, NIKALAC MX-279, NIKALAC MW-100LM, NIKALAC MX-750LM (above, trade name, manufactured by Sanwa Chemical Co., Ltd.). Two or more kinds of these may be contained. The thermal crosslinking agent preferably contains 0.01 to 50 parts by weight with respect to 100 parts by weight of the resin.

Examples of internal mold release agents include long-chain fatty acids such as lauric acid, stearic acid, and myristic acid; long-chain alcohols such as stearyl alcohol and myristyl alcohol; polyoxyalkylene alkyl ethers, fluoroalkyl epoxy Alkane adducts and so on.

Examples of the silane coupling agent include 3-aminopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, vinyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, etc. . From the viewpoint of storage stability, it is preferable to contain 0.01 to 5 parts by weight relative to 100 parts by weight of the polyimide precursor resin.

Examples of inorganic particles include silica fine particles, alumina fine particles, titanium oxide fine particles, zirconia fine particles, and the like.

The shape of the inorganic particles is not particularly limited, and examples include a spherical shape, an elliptical shape, a flat shape, a rod shape, and a fiber shape.

The particle size of the inorganic particles contained is not specifically defined, but in order to prevent light scattering, the particle size is preferably small. The average particle size is 0.5 to 100 nm, preferably in the range of 0.5 to 30 nm.

The content of the inorganic particles is preferably 1 to 200% by weight relative to the resin, and the lower limit is more preferably 10% by weight or more. The upper limit is more preferably 150 weight % Or less, more preferably 100% by weight or less, particularly preferably 50% by weight or less. As the content increases, the flexibility or folding resistance decreases.

As a method of mixing inorganic particles, various well-known methods can be used. For example, a mixture of inorganic particles or organic-inorganic filler sol and resin solution can be mentioned. Organic-inorganic filler sols are those in which inorganic fillers are dispersed in an organic solvent at a ratio of about 30% by weight. Examples of organic solvents include methanol, isopropanol, n-butanol, ethylene glycol, methyl ethyl ketone, and methyl ethyl ketone. Isobutyl ketone, propylene glycol monomethyl acetate, propylene glycol monomethyl ether, N,N-dimethylacetamide, N,N-dimethylformamide, N-methyl-2-pyrrolidine Ketones, 1,3-dimethylimidazolinone, γ-butyrolactone, etc.

The organic-inorganic filler sol is surface-treated by using a silane coupling agent, and the dispersibility of the inorganic filler in the resin is improved.

In the present invention, from the viewpoint of reducing CTE of the resin laminate film, inorganic particles may be contained. When laser peeling a resin film containing inorganic particles formed on a glass substrate, since the inorganic particles are not thermally decomposed by laser irradiation, the laser peelability may be significantly reduced. Therefore, in the resin laminated film of the present invention, it is preferable that the resin film 1 does not contain inorganic particles, and the resin film 2 contains inorganic particles. At this time, since a polyimide resin film with good laser releasability exists at the interface with the glass substrate, the resin laminate film containing inorganic particles in the resin film 2 can be easily peeled by laser peeling.

系紫外線吸收劑、苯甲酸酯系紫外線吸收劑、受阻胺系光安定劑等。於本發明之樹脂積層膜中，特佳為樹脂膜1含有紫外線 吸收劑。此時，由於對樹脂膜1照射紫外光時的光吸收係比不含紫外線吸收劑之情況高，故可減低雷射剝離所需要的照射能量。 Examples of ultraviolet absorbers include benzophenone-based ultraviolet absorbers, benzotriazole-based ultraviolet absorbers, and three

UV absorbers, benzoate UV absorbers, hindered amine light stabilizers, etc. In the resin laminated film of the present invention, it is particularly preferable that the resin film 1 contains an ultraviolet absorber. At this time, since the light absorption system when irradiating the resin film 1 with ultraviolet light is higher than that in the case where the ultraviolet absorber is not included, the irradiation energy required for laser peeling can be reduced.

Examples of the photoacid generator include quinonediazide compounds, sulfonium salts, phosphonium salts, diazonium salts, and iodonium salts. Among them, the quinonediazide compound is preferably used from the viewpoint of exhibiting an excellent dissolution suppression effect and obtaining a positive photosensitive resin composition with high sensitivity and low film thinning. Moreover, 2 or more types of photoacid generators may be contained. By this, the exposure caused by the i-line (wavelength 365nm), h-line (wavelength 405nm), and g-line (wavelength 436nm) of a general ultraviolet mercury lamp can be used to further increase the dissolution rate of the exposed and unexposed parts. In comparison, a high-sensitivity positive photosensitive resin composition can be obtained. The content of the photoacid generator is preferably 3-40 parts by weight relative to 100 parts by weight of the polyimide precursor. By setting the content of the photoacid generator in this range, higher sensitivity can be achieved. Furthermore, a sensitizer etc. may be contained as needed. Furthermore, as the developer used for the removal of the exposed part, it is preferably tetramethylammonium hydroxide, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, diethylaminoethanol, etc., which exhibit alkalinity. The aqueous solution of the compound. In addition, depending on the situation, it is also possible to add N-methyl-2-pyrrolidone and other amides, alcohols such as propanol, ethyl lactate, etc., singly or in combination, to these alkaline aqueous solutions. Esters, ketones such as cyclohexanone, lactones such as γ-butyrolactone, etc.

(Use of resin laminated film)

The resin laminate film of the present invention can be used as a TFT substrate provided with TFT on the resin film 2, or an organic EL element substrate provided with an organic EL element on the resin film 2, or as an organic EL element substrate provided on the resin film 2. Color filter Color filter substrate. For these, a supporting substrate may be provided on the resin film 1 side.

The resin laminate film of the present invention can be used for display elements such as liquid crystal displays, organic EL displays, electronic paper, etc., optical elements such as color filters or optical waveguides, solar cells, light-receiving elements such as CMOS, touch panels, and circuit substrates Wait. Particularly, in utilising these display elements, light-receiving elements, etc. as flexible elements that can be bent, the polyimide resin laminate film of the present invention can be preferably used as a flexible substrate. Furthermore, for display elements or optical elements (color filters, etc.) when the polyimide resin laminate film of the present invention is used as a flexible substrate, such as flexible display elements or flexible optical elements (optional Flexible color filters, etc.), etc., may also indicate "flexibility" before the device name. For example, the resin laminate film of the present invention can be produced on a supporting substrate such as glass, and a flexible TFT substrate provided with TFT on the resin film 2 and a flexible TFT substrate provided with an organic EL element on the resin film 2 can be used. Flexible organic EL element substrates, flexible color filter substrates with color filters, etc.

The production of display elements, light-receiving elements, circuit substrates, TFT substrates, etc. can be carried out by forming the resin laminate film of the present invention on a supporting substrate, peeling the resin laminate film from the supporting substrate, or without peeling the resin laminate film from the supporting substrate . The type of resin film 2 is not particularly limited, but from the viewpoint of heat resistance and mechanical properties, polyimide is preferred.

In the case of the former manufacturing method, the display element, light-receiving element, TFT circuit, etc. can be made on either the resin film 1 or the resin film 2, or on both resin films. In the case of the latter manufacturing method, due to the electrical After the circuit and so on, the self-supporting substrate is peeled off, so it has the advantage of being able to use the conventional single-piece manufacturing process. In addition, since the resin laminate film is fixed to the support substrate, it is suitable for manufacturing display elements, light-receiving elements, circuit substrates, TFT substrates, touch panels, etc., with good positional accuracy. In the following description, the latter method is often described as a representative example, but any one of them can be the former method.

In the resin laminated film of the present invention, an inorganic film can be produced on at least one side to form a gas barrier layer. As a substrate with a gas barrier layer, it can be suitably used as a substrate for display elements.

The gas barrier layer on the resin film achieves the task of preventing the penetration of water vapor or oxygen. Especially in organic EL devices, the deterioration of the device due to moisture is significant, so it is preferable to impart gas barrier properties to the substrate.

The substrate containing the resin laminated film of the present invention is flexible and has the characteristic of being able to be bent greatly. This flexible substrate is called a flexible substrate. The flexible substrate can be manufactured through at least the following steps (1), (2), and (4). In addition, a flexible substrate having an inorganic film on a polyimide resin film can be manufactured through at least the following steps (1) to (4).

(1) A step of manufacturing polyimide resin film A on a supporting substrate.

(2) A step of further laminating a resin film on the aforementioned resin film to form a resin laminated film.

(3) The step of forming an inorganic film on the aforementioned resin laminated film.

(4) The step of irradiating ultraviolet light from the side of the supporting substrate to peel off the aforementioned resin laminate film.

The steps of (1), (2), and (4) above are detailed as described in (1) to (3) in (Method for Manufacturing Resin Laminated Film).

The step (3) in the manufacturing steps of the flexible substrate is a step of forming an inorganic film on at least one surface of the resin laminate film. The resin laminate film can be peeled from the supporting substrate to produce a flexible substrate.

Furthermore, in the step (3), an inorganic film can be formed directly above the resin laminate film, or an inorganic film can be formed with other layers in between. Preferably, it is a method of forming an inorganic film directly above the resin laminated film. In addition, the place where the inorganic film is formed is not particularly limited. For example, the inorganic film may be formed on the resin film 1 after the step (1), may be formed on the resin film 2 after the step (2), or may be formed on the resin film 1 after the step (4). The peeling surface is formed on two films of the resin film 1 and the resin film 2.

唑等之耐熱塑膠薄膜；聚四氟乙烯或聚偏二氟乙烯等之氟樹脂；環氧樹脂、聚對苯二甲酸乙二酯或聚萘二甲酸乙二酯等之基材。於此等之中，從表面的平滑性、雷射剝離為可能、便宜之觀點等而言，較佳為玻璃。玻璃的種類係沒有特別的限制，但從金屬雜質減低之觀點而言，較佳為無鹼玻璃。 The supporting substrate when manufacturing the flexible substrate is preferably a self-supporting rigid one, and the surface on which the resin composition is applied is a smooth and heat-resistant substrate. The material is not particularly limited. For example, ceramics such as soda glass or alkali-free glass, silicon, quartz, alumina or sapphire can be mentioned; metals such as gallium arsenide, iron, tin, zinc, copper, aluminum, stainless steel, etc.; poly Imine or polybenzo

Heat-resistant plastic films such as azoles; fluororesins such as polytetrafluoroethylene or polyvinylidene fluoride; base materials such as epoxy resin, polyethylene terephthalate or polyethylene naphthalate. Among these, from the viewpoints of surface smoothness, possible laser peeling, and inexpensiveness, glass is preferred. The type of glass is not particularly limited, but from the viewpoint of reducing metal impurities, alkali-free glass is preferred.

As described above, when a flexible substrate is used for a substrate of a display element, since the substrate may require gas barrier properties, it is preferable to form an inorganic film on the resin laminated film. As the material of the inorganic film constituting the gas barrier layer, metal oxides, metal nitrides, and metal oxynitrides can be preferably used . For example, aluminum (Al), silicon (Si), titanium (Ti), tin (Sn), zinc (Zn), zirconium (Zr), indium (In), niobium (Nb), molybdenum (Mo), Metal oxides, metal nitrides and metal oxynitrides such as tungsten (Ta) and calcium (Ca). In particular, a gas barrier layer of metal oxides, metal nitrides, and metal oxynitrides containing at least Zn, Sn, and In has high bending resistance and is preferable. Furthermore, the gas barrier layer with the atomic concentration of Zn, Sn, and In of 20-40% has higher bending resistance and better. The composition in which silicon dioxide and aluminum oxide coexist in the gas barrier layer also has good bending resistance and is preferable.

These inorganic gas barrier layers can be produced by, for example, a sputtering method, a vacuum vapor deposition method, an ion plating method, a plasma CVD method, or the like, by a vapor deposition method in which a material is deposited in a vapor phase to form a film. Among them, in the sputtering method, by performing reactive sputtering in which a metal target is sputtered in an oxygen-containing environment, the film forming speed can be increased.

The formation of the gas barrier layer may be performed on a laminate composed of a supporting substrate and a resin laminate film, or may be performed on a self-supporting film peeled from the supporting substrate.

The film forming temperature of the gas barrier layer is preferably set to 80~400°C. In order to improve the gas barrier performance, it is advantageous to select a higher film forming temperature. However, if the film forming temperature is high, the bending resistance may decrease. Therefore, in applications where bending resistance is important, the film forming temperature of the gas barrier layer is preferably 100 to 300°C. In the resin laminated film of the present invention, when the resin film 2 is polyimide, since the resin laminated film has high heat resistance, the substrate temperature can be increased to form a gas barrier layer. In addition, even if the gas barrier layer is formed at a high temperature (for example, 300°C), defects such as wrinkles do not occur in the film.

The number of layers of the gas barrier layer is not limited, it can be only one layer, or It is a multi-layer of 2 or more layers. As an example of a multilayer film, the first layer is SiO, the second layer is a gas barrier layer composed of SiN, or the first layer is SiO/AlO/ZnO, and the second layer is a gas barrier layer composed of SiO Floor.

Various organic solvents are used in the steps of forming layers with various functions, such as organic EL light-emitting layers, on the gas barrier layer of the flexible substrate, and manufacturing display elements or optical elements. For example, in the case of a color filter (hereinafter, also referred to as CF), a gas barrier layer is formed on a resin laminate film, and then colored pixels or a black matrix are formed to make CF. At this time, when the solvent resistance of the gas barrier layer is poor, the gas barrier performance is reduced. Therefore, it is preferable to impart solvent resistance to the uppermost gas barrier layer. For example, the uppermost gas barrier layer is preferably made of silicon oxide.

The composition analysis of the gas barrier layer is performed by quantitatively analyzing each element using X-ray photoelectron spectroscopy (XPS method).

The total thickness of the gas barrier layer is preferably 20 to 600 nm, more preferably 30 to 300 nm.

The thickness of the gas barrier layer can usually be measured by cross-sectional observation with a transmission electron microscope (TEM).

When the composition of the boundary area between the upper and lower layers of the gas barrier layer changes obliquely, and a clear interface cannot be recognized by TEM vision, first, analyze the composition in the thickness direction to obtain the concentration distribution of the elements in the thickness direction. , Based on the information of the concentration distribution, the boundary of the layer and the thickness of the layer are obtained. The procedure of composition analysis in the thickness direction, the boundary of each layer and the definition of the thickness of the layer are described below.

First, observe the cross-section of the gas barrier layer with a transmission electron microscope to measure the overall thickness. Secondly, using elements in the depth direction The composition analysis of is the following possible measurement, and the concentration distribution of the element corresponding to the thickness position of the gas barrier layer (the concentration profile in the thickness direction) is obtained. The composition analysis methods that can be used at this time include electron energy loss spectroscopy (hereinafter referred to as EELS analysis), and Energy-dispersive X-ray spectroscopy (hereinafter referred to as EDX analysis), secondary ion mass spectrometry (hereinafter referred to as SIMS analysis), X-ray photoelectron spectroscopy (described as XPS analysis), Auger electron spectroscopy (Aug erelectron spectroscopy) (hereinafter referred to as AES analysis), but from the viewpoint of sensitivity and accuracy, EELS analysis is the best. Therefore, first perform EELS analysis, and use the following order (EELS analysis → EDX analysis → SIMS analysis → XPS analysis → AES analysis). For components that cannot be identified by higher analysis, lower analysis data can be used.

The CF can be obtained by disposing a black matrix and colored pixels on a flexible substrate using the resin laminated film of the present invention. Since this CF uses a resin film in the base material, it has the characteristics of light weight, resistance to breakage, and flexibility. The resin used in at least one of the black matrix and the colored pixel layer preferably contains a polyimide resin. Furthermore, from the viewpoint of reduction in reflectance and heat resistance, it is preferable that the black matrix is composed of a low optical density layer and a high optical density layer formed on the low optical density layer, and the low optical density layer and the high optical density layer The resin used in at least one layer of the optical density layer contains polyimide resin.

In the resin laminated film of the present invention, when the resin film 2 is polyamide In the case of imine, since the solvent of the polyimide precursor has high chemical resistance to general polar aprotic solvents, polyimide resin can be used in the black matrix and colored pixel layer. Furthermore, even when the gas barrier layer is formed on the black matrix and colored pixel layer, the polyimide resin of the black matrix and colored pixel layer has high heat resistance, so gas is generated during the formation of the gas barrier layer. It is possible to manufacture a gas barrier layer with high gas barrier properties. In addition, in the pattern processing of the black matrix and the colored pixel layer, since a polyimide precursor that is soluble in an alkaline aqueous solution can be used, it is advantageous for the formation of fine patterns.

An example of the CF configuration is explained in the figure. Fig. 1 shows the basic structure of CF including the resin laminated film of the present invention formed on a supporting substrate. From then on, the support substrate (symbol: 1) was peeled off by the aforementioned peeling method, and a CF using the resin laminated film of the present invention as a substrate was obtained.

A resin laminated film (symbol: 2) composed of polyimide resin film A (symbol: 2A) and resin film (symbol: 2B) is formed on a supporting substrate (symbol: 1), and a black matrix ( Symbol: 3), red coloring pixel (symbol: 4R), green coloring pixel (symbol: 4G), and blue coloring pixel (symbol: 4B). Furthermore, an overcoat layer can also be formed on the colored pixels. Furthermore, it can also be formed as a gas barrier layer of an inorganic film. The place where the gas barrier layer is formed is not particularly limited. For example, it can be formed on a resin laminate film (symbol: 2), a black matrix (symbol: 3) or a layer of colored pixels, or it can be formed The overcoat layer existing on the surface of the color filter can also be formed on both the resin laminate film (symbol: 2) and the overcoat layer. In addition, the number of layers of the gas barrier layer is not limited, and it may be only one layer or multiple layers of two or more layers. As an example of a multilayer film, the first layer is SiO, the second layer is a gas barrier layer made of SiN, or the first layer is SiO/AlO/ZnO, the second layer is a gas barrier layer made of SiO.

The black matrix is preferably a black matrix composed of resin in which black pigments are dispersed. Examples of black pigments include carbon black, titanium black, titanium oxide, titanium oxynitride, titanium nitride, or iron tetroxide. In particular, carbon black and titanium black are suitable. In addition, a red pigment, a green pigment, and a blue pigment may be mixed and used as a black pigment.

In the manufacture of the black matrix, a black composition containing the aforementioned black pigment, preferably containing a resin, and more preferably containing a solvent is used. Furthermore, it is preferable to form a black matrix by patterning the black resin composition. The black composition system may be non-photosensitive or photosensitive. As a method of patterning, machining, dry etching, sandblasting, photolithography, etc. are mentioned, and light capable of high-definition patterning is preferred. Lithography. As a patterning method of photolithography, the black resin composition itself can be used as a photosensitive material for patterning. Alternatively, the photolithography method can be performed by laminating a photoresist different from the black resin composition to form the black resin. The object is patterned to form a black matrix. In photolithography, an exposure step and a development step are performed to perform patterning.

As the resin used for the resin black matrix, a polyimide resin is preferable from the viewpoint of heat resistance and the ease of formation of a fine pattern. The polyimide resin is preferably a polyimide resin synthesized from an acid dianhydride and a diamine, which is thermally cured after pattern processing, to form a polyimide resin. In addition, as examples of acid dianhydrides, diamines, and solvents, those listed under the item of the aforementioned "resin film 1" can be used.

In order to form a black matrix containing polyimide resin, it is generally a photosensitive material composed of at least polyimide acid, black pigment, and solvent. After the black composition is coated on the substrate, it is dried by air drying, heat drying, vacuum drying, etc., to form a non-photosensitive polyamide acid black film. A positive photoresist is used to form the desired pattern, and then the photoresist is peeled off by alkali , Finally, by heating at 200~300°C for 1 minute to 3 hours, the colored pixels are hardened (polyimidized).

As the resin used for the resin black matrix, photosensitive acrylic resin can also be used. In the production of the black matrix, a black matrix containing an alkali-soluble acrylic resin dispersed with black pigment, a photopolymerizable monomer, a polymerization initiator, and a solvent is used. Composition.

Examples of alkali-soluble acrylic resins include copolymers of unsaturated carboxylic acids and ethylenically unsaturated compounds. Examples of unsaturated carboxylic acids include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, vinyl acetic acid, or acid anhydride.

Examples of photopolymerizable monomers include trimethylolpropane tri(meth)acrylate, neopentylerythritol tri(meth)acrylate, tripropenyl formaldehyde, neopentaerythritol tetra(meth)acrylate Base) acrylate, dineopentaerythritol hexa(meth)acrylate or dineopentaerythritol penta(meth)acrylate.

Examples of photopolymerization initiators include diphenyl ketone, N,N'-tetraethyl-4,4'-diamino diphenyl ketone, 4-methoxy-4'-dimethyl Amino benzophenone, 2,2-diethoxyacetophenone, α-hydroxyisobutyl phenone, thioxanthone or 2-chlorothioxanthone.

Examples of solvents for dissolving photosensitive acrylic resins include propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethyl acetylacetate, and methyl-3-methoxypropionate. , Ethyl-3-ethoxypropionate, methoxybutyl acetate or 3-methyl-3-methoxybutyl acetate ester.

In order to suppress the decrease in visibility due to external light reflection, the black matrix is preferably a laminated resin black matrix composed of a low optical density layer and a high optical density layer formed on the low optical density layer. Furthermore, the so-called low optical density layer refers to a layer whose optical density is not zero and is substantially opaque, and the value of the optical density per unit thickness is smaller than the optical density per unit thickness of the high optical density layer. The resin system constituting the aforementioned laminated resin black matrix is not particularly limited, but from the viewpoint of patterning the low optical density layer and the high optical density layer in batches, the low optical density layer is preferably a polyimide resin, and the high optical density layer is preferably a polyimide resin. The optical concentration layer is preferably an acrylic resin. Furthermore, in order to reduce the reflectance, it is more preferable to include fine particles in the resin black matrix.

After the black matrix is formed, colored pixels are formed. The coloring pixels are composed of red, green, and blue coloring pixels. Furthermore, in addition to the three-color colored pixels, the brightness of the white display of the display device can also be improved by forming a colorless, transparent or extremely lightly colored fourth color pixel.

CF coloring pixels can use resins containing pigments or dyes as colorants.

Examples of pigments used in red coloring pixels include PR254, PR149, PR166, PR177, PR209, PY138, PY150, or PYP139, and examples of pigments used in green coloring pixels include PG7, PG36, PG58, PG37, PB16, PY129, PY138, PY139, PY150, or PY185, as examples of the pigment used in the blue coloring pixel, PB15:6 or PV23 can be cited.

As an example of the blue dye, C.I. Basic Blue (BB) 5 , BB7, BB9, or BB26. Examples of red dyes include C.I. Acid Red (AR) 51, AR87, or AR289, and examples of green dyes include C.I. Acid Green (AG) 25 and AG27.

Examples of resins used in the red, green and blue colored pixels include acrylic resin, epoxy resin, or polyimide resin. From the viewpoint of heat resistance, a polyimide resin is preferable, and in order to reduce the production cost of CF, a photosensitive acrylic resin may also be used.

In order to form a colored pixel composed of polyimide resin, generally a non-photosensitive color paste composed of at least polyimide acid, colorant, and solvent is coated on a substrate and then dried by air, heating, Dry by vacuum drying, etc., to form a non-photosensitive polyamide acid colored film, use a positive photoresist to form the desired pattern, peel off the photoresist with alkali, and finally heat it at 200-300°C for 1 minute to 3 hours. A method to harden the colored pixels (polyimide).

The photosensitive acrylic resin generally contains an alkali-soluble acrylic resin, a photopolymerizable monomer, and a photopolymerization initiator.

Examples of alkali-soluble acrylic resins include copolymers of unsaturated carboxylic acids and ethylenically unsaturated compounds. Examples of unsaturated carboxylic acids include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, vinyl acetic acid, or acid anhydride.

Examples of photopolymerizable monomers include trimethylolpropane tri(meth)acrylate, neopentylerythritol tri(meth)acrylate, tripropenyl formaldehyde, neopentaerythritol tetra(meth)acrylate Base) acrylate, dineopentaerythritol hexa(meth)acrylate or dineopentaerythritol penta(meth)acrylate.

Examples of photopolymerization initiators include diphenyl ketone, N,N'-tetraethyl-4,4'-diaminodiphenyl ketone, 4-methoxy-4'-dimethylaminodiphenyl ketone, 2,2-diethoxybenzene Ethyl ketone, α-hydroxyisobutyl phenone, thioxanthone or 2-chlorothioxanthone.

Examples of solvents for dissolving photosensitive acrylic resins include propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethyl acetylacetate, and methyl-3-methoxypropionate. , Ethyl-3-ethoxypropionate, methoxybutyl acetate or 3-methyl-3-methoxybutyl acetate.

In order to flatten the surface of the CF on which the black matrix and colored pixels are formed, an overcoat layer may be further formed on the surface of the CF. Examples of the resin used in the formation of the overcoat layer include epoxy resin, acrylic modified epoxy resin, acrylic resin, silicone resin, or polyimide resin. As the thickness of the outer layer, it is preferable that the surface has a flat thickness, more preferably 0.5 to 5.0 μm, and still more preferably 1.0 to 3.0 μm.

The CF system containing the resin laminated film of the present invention can be manufactured through at least the following steps.

(1) A step of manufacturing polyimide resin film A on a supporting substrate.

(2) A step of further laminating a resin film on the aforementioned resin film to form a resin laminated film.

(3) The step of forming a black matrix on the aforementioned resin laminated film.

(4) The step of forming colored pixels on the aforementioned resin laminated film.

(5) The step of irradiating ultraviolet light from the side of the supporting substrate to peel off the aforementioned resin laminate film.

The steps (1), (2), and (5) above are detailed as described in (1) to (3) in (Method for Manufacturing Resin Laminated Film).

The steps (3) and (4) in the above-mentioned CF manufacturing steps are steps of forming a black matrix and colored pixels on the resin laminate film. As mentioned above, light lithography is used in the pattern formation of the black matrix or colored pixels. At present, as a liquid crystal display or an organic EL display, a high-definition of 300ppi or more is required, and the same or higher performance is also required in a flexible display panel. In order to achieve such high resolution, high-precision pattern formation is required. When the black matrix or colored pixels are formed on the resin laminated film formed on the support substrate to produce CF, since the current technology of using the glass substrate as the support substrate to produce CF can be used, it is the same as the case of making CF on the self-supporting film In contrast, high-definition patterns can be formed.

Furthermore, in the steps (3) and (4), a black matrix or colored pixels can be formed directly above the resin laminate film, or they can be formed with other layers in between.

In the above-mentioned manufacturing step of CF, it may further include a step of manufacturing an inorganic film such as a gas barrier layer. The place where the inorganic film is formed is not particularly limited. For example, it can be formed on a resin laminate film, it can be formed on a black matrix or a colored pixel layer, it can also be formed on an overcoat layer that exists on the surface of a color filter, or it can be formed on a resin laminate film and overcoat. Both on the layer. In addition, the number of layers of the inorganic film is not limited, and it may be only one layer or multiple layers of two or more layers. As an example of a multilayer film, the first layer is SiO and the second layer is an inorganic film composed of SiN, or the first layer is SiO/AlO/ZnO and the second layer is an inorganic film composed of SiO.

Next, an example of the CF manufacturing method of the present invention will be explained more specifically. Using the above method, the resin laminated film and gas barrier layer of the present invention are produced on the supporting substrate. On it, use a spin coater or a mouth mode coater In other methods, a black matrix paste made of polyamide acid in which a black pigment made of carbon black or titanium black is dispersed is applied so that the thickness after curing becomes 1 μm, and then dried under reduced pressure to 60 Pa or less. Use 110~140℃ hot air oven or hot plate for semi-curing.

Use a spin coater or mouth mode coater to coat the positive photoresist with a thickness of 1.2μm after pre-baking, and then dry it under reduced pressure until 80Pa. Use a hot air oven at 80~110℃ or The hot plate is pre-baked to form a photoresist film. Then, by using a proximity exposure machine or a projection exposure machine, etc., through a photomask, the exposure is selectively carried out with ultraviolet rays, and then 1.5 to 3% by weight of potassium hydroxide or tetramethylammonium hydroxide and other alkaline developing solutions are used. Medium immersion for 20 to 300 seconds to remove the exposed part. After peeling off the positive photoresist with a stripping solution, use a hot air oven or hot plate at 200~300℃ for 10~60 minutes to convert polyamide acid into polyimide to form a resin black matrix.

The colored pixels are produced using colorants and resins. When a pigment is used as a colorant, a polymer dispersant and a solvent are mixed with the pigment, and a polyamide acid is added to the dispersion liquid that has been subjected to the dispersion treatment. On the other hand, when a dye is used as a coloring agent, it is produced by adding a solvent and polyamide acid to the dye. The total solid content at this time is the sum of the polymer dispersant of the resin component, the polyamide acid, and the coloring agent.

Apply the obtained coloring agent composition on a resin laminate film formed with a resin black matrix, using a spin coater or die coater, etc., so that the thickness after heat treatment becomes the target thickness of 0.8 to 3.0 μm After coating, it is dried under reduced pressure and pre-baked in a hot air oven or hot plate at 80~110℃ to form a coating film of coloring agent.

Then, use a spin coater or a die coater to coat the positive photoresist so that the thickness after pre-baking becomes 1.2μm, and then dry it under reduced pressure. Use a hot air oven at 80 to 110°C or heat The board is pre-baked to form a photoresist film. Then, by using a proximity exposure machine or a projection exposure machine, etc., through a photomask, the exposure is selectively carried out with ultraviolet rays, and then 1.5 to 3% by weight of potassium hydroxide or tetramethylammonium hydroxide and other alkaline developing solutions are used. Medium immersion for 20 to 300 seconds to remove the exposed part. After peeling off the positive photoresist with the stripping solution, use a hot air oven or hot plate at 200~300℃ to heat for 10~60 minutes to convert polyamide acid into polyimide to form a colored pixel. For each color of the coloring pixels, using the prepared coloring agent composition, for the red coloring pixel, the green coloring pixel, and the blue coloring pixel, the patterning steps as described above are performed in sequence. In addition, the patterning order of the colored pixels is not particularly limited.

Then, use a spin coater or die coater, etc., after coating the polysiloxane resin, vacuum drying, pre-baking with a hot air oven or hot plate at 80~110℃, and hot air at 150~250℃ The oven or hot plate is heated for 5-40 minutes to form an overcoat layer, whereby the CF pixels of the present invention can be produced.

As described above, the resin laminate film of the present invention has a large light absorption in the ultraviolet range of the resin film 1, so that the irradiation energy required for peeling can be reduced. In addition, when the CTE of the resin laminate film of the present invention is low, for example, 30 ppm/°C or less, the warpage of the substrate when the resin laminate film is formed on the support substrate can be reduced. Therefore, the focus shift in the photolithography step during the formation of the black matrix or colored pixels can be reduced, and as a result, the CF can be manufactured with high precision. Furthermore, by reducing the CTE, the color filter after peeling can be reduced Curling can suppress pixel defects after peeling.

The resin laminated film system of the present invention can be applied to the base material of a TFT substrate. That is, a TFT substrate having TFTs on the resin laminated film of the present invention can be obtained. Since this TFT substrate uses a resin film as a base material, it has characteristics such as light weight and resistance to cracking.

An example of the structure of TFT is explained with the figure. Fig. 2 shows the basic structure of a TFT including the resin laminated film of the present invention formed on a supporting substrate. From then on, by peeling the support substrate (symbol: 1) by the aforementioned peeling method, a TFT using the resin laminated film (symbol: 2') of the present invention as a substrate can be obtained. A resin laminated film (symbol: 2') composed of polyimide resin film A (symbol: 2A') and resin film (symbol: 2B') is formed on the supporting substrate (symbol: 1), and further A gas barrier layer (symbol: 5) is formed as an inorganic film, and a TFT (symbol: 6) and a planarization layer (symbol: 7) are formed thereon.

The TFT substrate using the resin laminated film of the present invention can be manufactured through at least the following steps.

(1) A step of manufacturing polyimide resin film A on a supporting substrate.

(2) A step of further laminating a resin film on the aforementioned resin film to form a resin laminated film.

(3) Steps of forming a gas barrier layer on the aforementioned resin laminated film

(4) The step of forming a TFT on the aforementioned resin laminated film.

(5) The step of irradiating ultraviolet light from the side of the supporting substrate to peel off the aforementioned resin laminate film.

The steps (1), (2), and (5) above are detailed as described in (1) to (3) in (Method for Manufacturing Resin Laminated Film).

The steps (3) and (4) in the above-mentioned manufacturing steps of the TFT substrate are the steps of forming a gas barrier layer on the resin laminate film, and then forming the TFT. Furthermore, in the step (3) or (4), a gas barrier layer or TFT can be formed directly above the resin laminate film, or it can be formed with other layers in between. Preferably, it is a method of forming a gas barrier layer directly above the resin laminate film and forming a TFT thereon.

Examples of the semiconductor layer for forming TFTs include amorphous silicon semiconductors, polycrystalline silicon semiconductors, ^{oxide semiconductors represented by In-Ga-ZnO-} ₄ , organic semiconductors represented by fused pentacene or polythiophene, and carbon nanotubes. Carbon materials such as rice tubes. For example, using the resin laminate film of the present invention as a substrate, a gas barrier layer, a gate electrode, a gate insulating film, a semiconductor layer, an etching stop film, and a source are sequentially formed by a well-known method. Drain the electrode, and fabricate the bottom gate type TFT.

Through the above-mentioned steps, a TFT substrate using the resin laminated film of the present invention can be manufactured. Such a TFT substrate can be used as a drive substrate for display elements such as liquid crystal elements, organic EL elements, and electronic paper.

The manufacturing temperature of TFT depends on the type of semiconductor layer. However, in the case of polycrystalline silicon semiconductor or oxide semiconductor, it is advantageous to select a higher manufacturing temperature in order to improve mobility or reliability. Generally speaking, it must be 500°C or higher in polycrystalline silicon semiconductors, and 300°C or higher in oxide semiconductors. In the resin laminated film of the present invention, when the resin film 2 is polyimide, since the resin laminated film has high heat resistance, it is possible to manufacture high-temperature TFTs. In addition, when the acid dianhydride residues in the polyimide resin film A contained in the resin film 1 are aromatic acid dianhydride residues, the heat resistance of the resin film 1 becomes high, because it can reduce There is less exhaust during the above-mentioned high-temperature semiconductor manufacturing steps, so a high-quality TFT substrate with fewer element defects can be obtained. In addition, when the aforementioned aromatic acid dianhydride residue is a group derived from pyromellitic dianhydride or 3,3',4,4'-biphenyltetracarboxylic dianhydride, the heat resistance is further increased. good.

As described above, the resin laminate film of the present invention has a high light absorption in the ultraviolet range of the resin film 1, so that the irradiation energy required for peeling can be reduced. In the manufacture of TFT substrates, in the gate electrode, gate insulating film, semiconductor layer, etching stop film, source. In the formation of the drain electrode, photolithography is mainly used. Furthermore, when the CTE of the resin laminate film of the present invention is low, for example, 30 ppm/°C or less, preferably 10 ppm/°C or less, the warpage of the substrate when the resin laminate film is formed on the supporting substrate can be reduced as described above. Therefore, since the focus shift in the photolithography step can be reduced, the TFT can be manufactured with high precision. As a result, a TFT substrate with good driving performance can be obtained. In addition, since the curl of the TFT substrate after peeling can be reduced, it is possible to prevent the breakage of the TFT element after peeling.

The flexible substrate using the resin laminated film of the present invention can be used as a substrate for a touch panel. For example, a transparent conductive film can be formed by forming a transparent conductive layer on at least one surface of the resin laminated film of the present invention, and the transparent conductive films can be laminated on each other using an adhesive or adhesive to form a touch panel.

As the transparent conductive layer, well-known metal films, metal oxide films, etc., carbon nanotubes or carbon materials such as graphene can be used, but among them, from the viewpoints of transparency, conductivity and mechanical properties, it is preferable to use Metal oxide film. As the aforementioned metal oxide film, for example, tin, tellurium, cadmium, molybdenum, tungsten, fluorine, zinc, germanium, etc. are added as inclusions. Metal oxide films such as indium oxide, cadmium oxide and tin oxide are added as inclusions of aluminum. Among them, a thin film containing 2 to 15% by mass of tin oxide or zinc oxide indium oxide is preferably used because of its excellent transparency and conductivity.

The film forming method of the transparent conductive layer mentioned above can be any method as long as it can form the target thin film, but it is suitable for the vapor-phase method such as sputtering method, vacuum evaporation method, ion plating method, plasma CVD method, etc. The vapor deposition method in which materials are deposited to form a film, etc. Among them, particularly excellent conductivity can be obtained. From the viewpoint of transparency, it is preferable to form a film using a sputtering method. In addition, the film thickness of the transparent conductive layer is preferably 20 to 500 nm, more preferably 50 to 300 nm.

In addition, the patterning method of the transparent conductive layer is not particularly limited, and examples include wet etching using photoresist and etching solution, dry etching using laser, and the like.

The flexible substrate using the resin laminated film of the present invention can be used for display elements such as liquid crystal displays, organic EL displays, electronic paper, and light-receiving elements such as solar cells and CMOS. In particular, it is preferable to use the flexible substrate of the present invention in terms of utilizing such display elements or light-receiving elements as flexible devices that can be bent.

As an example of the manufacturing process of a display element or a light-receiving element, a resin laminate film formed on a substrate may be used to form circuits and functional layers required for the display element or the light-receiving element, and further irradiate ultraviolet light to peel the resin from the substrate. Laminated film.

An organic EL element as an example of a display element, Figure 3 shows an organic EL element (top emission method, red, green, and blue light-emitting organic EL). A resin laminate film (symbol: 2') composed of polyimide resin film A (symbol: 2A') and resin film (symbol: 2B') is formed on the support substrate (symbol: 1), and further A gas barrier layer (symbol: 5) formed as an inorganic film, on which a circuit of TFT (symbol: 6) and an organic EL light-emitting layer (symbol: 11R, 11G, 11B), etc. are formed. TFT (symbol: 6) circuit and organic EL light-emitting layer (symbol: 11R, 11G, 11B) are composed of the following: TFT (symbol: 6) composed of amorphous silicon, low-temperature polysilicon, oxide semiconductor, etc. ; And a planarization layer (symbol: 7); a first electrode (symbol: 8) composed of Al/ITO, etc.; an insulating layer (symbol: 9) covering the end of the first electrode (symbol: 8); Red, green and blue organic EL light emitting layer (symbol: 11R, 11G, 11B) composed of hole injection layer, hole transport layer, light emitting layer, electron transport layer, and electron injection layer (symbol: 11R, 11G, 11B); second electrode composed of ITO, etc. (Symbol: 10), and is sealed with a sealing film (symbol: 12). The resin laminate film (symbol: 2') is peeled from the supporting substrate (symbol: 1) by irradiating ultraviolet light, and it can be used as an organic EL device.

The organic EL element containing the resin laminated film of the present invention can be manufactured through at least the following steps.

(1) A step of manufacturing polyimide resin film A on a supporting substrate.

(2) A step of further laminating a resin film on the aforementioned resin film to form a resin laminated film.

(3) The step of forming an organic EL element on the aforementioned resin laminated film.

(4) The step of irradiating ultraviolet light from the side of the supporting substrate to peel off the aforementioned resin laminate film.

The steps of (1), (2), and (4) above are detailed as described in (1) to (3) in (Method for Manufacturing Resin Laminated Film).

The step (3) of the above-mentioned organic EL device manufacturing steps is formed in accordance with: TFT (symbol: 6) composed of amorphous silicon, low-temperature polysilicon, oxide semiconductor, etc.; and planarization layer (symbol: 7) ; A first electrode (symbol: 8) composed of Al/ITO, etc.; an insulating layer (symbol: 9) covering the end of the first electrode (symbol: 8); a hole injection layer, a hole transport layer, White or various colors (red, green, blue, etc.) organic EL light-emitting layer (symbol: 11W, 11R, 11G, 11B) composed of light-emitting layer, electron transport layer, and electron injection layer; second composed of ITO, etc. Electrode (symbol: 10). At this time, it is preferable to form an inorganic gas barrier layer (symbol: 5) on the resin laminate film (symbol: 2') before forming the TFT circuit and the organic EL light-emitting layer, and it is also preferable to After the organic EL light-emitting layer is formed, it is sealed with a sealing film (symbol: 12).

Furthermore, the light extraction method may be either a bottom emission method in which light is extracted on the TFT substrate side, or a top emission method in which light is extracted on the sealing film side.

The organic EL element containing the resin laminate film of the present invention and/or the CF containing the resin laminate film of the present invention can be preferably used as an organic EL display equipped with them. For example, by combining a white light-emitting organic EL element using the resin laminate film of the present invention in a substrate and CF including the resin laminate film of the present invention, an organic EL display with full color display can be obtained. In addition, for the purpose of improving color purity, a combination of a red, green, and blue light-emitting organic EL element using the resin laminate film of the present invention in a substrate and CF containing the resin laminate film of the present invention may be combined.

Fig. 4 shows an example of the organic EL display formed by bonding the CF and the white light-emitting organic EL element of the present invention. As its manufacture As an example of the steps, the following methods can be cited. By the aforementioned manufacturing method, the CF 20 of the present invention is formed on the first supporting substrate (not shown). In addition, by the aforementioned method, an organic EL element 30 having a resin laminate film as a substrate is formed on a second supporting substrate (not shown). Then, the CF (symbol: 20) and the organic EL element (symbol: 30) are bonded via the adhesive layer 13. Then, by irradiating the first and second support substrates with ultraviolet light from the support substrate side, respectively, the first and second support substrates are peeled off.

The adhesive layer system is not particularly limited. For example, an adhesive, an adhesive, and an adhesive can be cured by light or heat. The resin system of the subsequent layer is not particularly limited, and examples thereof include acrylic resins, epoxy resins, urethane resins, polyamide resins, polyimide resins, and silicone resins.

[Example]

Examples etc. are given below to illustrate the present invention, but the present invention is not limited by these examples.

(1) Production of polyimide resin laminated film (on glass substrate)

A 100mm×100mm×0.7mm thick glass substrate (AN-100 Asahi Glass Co., Ltd.) was used as a support substrate. For this, a spin coater MS-A200 manufactured by MIKASA (stock) was used for pre-treatment at 140°C×4 minutes. After baking, the thickness becomes the specified thickness (0.15, 0.75, 1.5, 3.0, 7.5, 15.0μm), adjust the number of rotations, and spin-coat the varnish (synthesis examples 1-19). Then, using a hot plate D-SPIN made by Dainippon Screen Co., Ltd., a pre-baking treatment was performed at 140° C. for 4 minutes. For the pre-baked coating film, use a passive oven (INH-21CD manufactured by Koyo Thermal Systems Co., Ltd.) under a nitrogen flow (oxygen concentration below 20 ppm), and raise the temperature to 300°C or 400°C at 3.5°C/min. , Hold for 30 minutes, to Cool down to 50°C at 5°C/min to produce a resin film 1. Next, the resin film 1 was spin-coated with a varnish (Synthesis Examples 20-22, Preparation Examples 1 and 2) so that the thickness after the prebaking became 15.0 μm in the same manner as described above. Then, in the same manner as described above, a pre-baking treatment/baking in a passivation oven is performed, and the resin film 2 is produced on the resin film 1.

(2) Production of polyimide resin film (on glass substrate)

A 100mm×100mm×0.7mm thick glass substrate (AN-100 Asahi Glass Co., Ltd.) was used as a support substrate. For this, a spin coater MS-A200 manufactured by MIKASA (stock) was used for pre-treatment at 140°C×4 minutes. When the thickness after baking becomes 15.0μm, the number of rotations is adjusted, and the varnish is spin-coated (Synthesis Examples 1-22, Preparation Examples 1 and 2). Then, using a hot plate D-SPIN made by Dainippon Screen Co., Ltd., a pre-baking treatment was performed at 140° C. for 4 minutes. For the pre-baked coating film, use an inert oven (INH-21CD manufactured by Koyo Thermal Systems Co., Ltd.), and heat up to 300°C at 3.5°C/min under a nitrogen flow (oxygen concentration below 20ppm) Or, keep it at 400°C for 30 minutes, and cool it down to 50°C at 5°C/min to produce a polyimide resin film. The thickness of the obtained polyimide resin film was 10.0 μm.

(3) Measurement of light transmittance of polyimide resin laminated film

Using an ultraviolet-visible spectrophotometer (MultiSpec1500 manufactured by Shimadzu Corporation), the light transmittance at 400 nm was measured. In addition, the polyimide resin laminated film on the glass substrate prepared in (1) was used for the measurement.

(4) Determination of absorbance of diamine solution

Using an ultraviolet-visible spectrophotometer (MultiSpec1500 manufactured by Shimadzu Corporation), the absorbance at 266 nm, 308 nm, 343 nm, 351 nm, and 355 nm was measured. Furthermore, a quartz cell with a light path length of 1 cm was used to measure a diamine solution (solvent: NMP) ^{with a concentration of 1×10 -4 mol/L.}

(5) Measurement of the light transmittance of the resin film 1 in the polyimide resin laminated film

)，製作膜厚100nm的樹脂膜1。使用顯微紫外可見近紅外分光光度計(日本分光(股)製MSV-5100)，測定作成為厚度100nm之膜時的樹脂膜1在266nm、308nm、343nm、351nm、355nm的透光率。在5處進行同樣的蝕刻與透光率測定，將彼等之平均值設作透光率。 For the polyimide resin laminate film formed on a glass substrate by the method described in (1), use a GD-OES analyzer (GD-Profiler 2 manufactured by Horiba Manufacturing Co., Ltd.) from the resin film 2 to the resin film 1 Carry out etching (diameter 5mm

), a resin film 1 with a film thickness of 100 nm was produced. Using a micro-ultraviolet-visible-near-infrared spectrophotometer (MSV-5100, manufactured by JASCO Corporation), the light transmittance at 266 nm, 308 nm, 343 nm, 351 nm, and 355 nm of the resin film 1 when it was made into a film with a thickness of 100 nm was measured. Perform the same etching and light transmittance measurement at 5 places, and set their average value as the light transmittance.

(6) Laser peel test

For the polyimide resin laminate film obtained by the method described in (1), the polyimide resin film obtained by the method described in (2), and the CF, TFT substrate, and organic EL produced by the method described later In the display, a 308 nm excimer laser (shape: 21 mm×1.0 mm) was irradiated from the glass substrate side, and a laser peel test was performed. The laser system is irradiated while staggering 0.5mm at a time in the short axis direction. When the incision was introduced along the edge of the irradiation area, the irradiation energy required for peeling was measured as the energy for film peeling, and the evaluation was performed using the following criteria.

A: The irradiation energy is 230 mJ/cm ² or less.

B: The irradiation energy exceeds 230 mJ/cm ² and is 250 mJ/cm ² or less.

C: The irradiation energy exceeds 250 mJ/cm ² and is 270 mJ/cm ² or less.

D: The irradiation energy exceeds ^{270 mJ/cm 2} and is 290 mJ/cm ² or less.

E: The irradiation energy exceeds 290 mJ/cm ² .

(7) Measurement of linear thermal expansion coefficient (CTE) and glass transition temperature (Tg)

A thermomechanical analysis device (EXSTAR6000 TMA/SS6000 manufactured by SII Nano Technology Co., Ltd.) was used for the measurement under a nitrogen stream. The heating method is carried out under the following conditions. In the first stage, the temperature is raised to 150°C at a temperature increase rate of 5°C/min to remove the adsorbed water of the sample, and in the second stage, it is air-cooled to room temperature at a temperature decrease rate of 5°C/min. In the third stage, the measurement is performed at a heating rate of 5°C/min to obtain CTE and Tg. Furthermore, CTE is the average value of 50°C~200°C in the third stage. In addition, in the measurement, the method described in (6) was used for laser peeling (1) the polyimide resin laminated film on the glass substrate and (2) the polyimide resin film made on the glass substrate. The obtained polyimide resin laminated film (Examples 1 to 29, Comparative Examples 1 to 3) and the polyimide resin film (Synthesis Examples 1 to 23, Preparation Examples 1 and 2). Furthermore, the difference between the CTE of the polyimide resin laminated film (resin film 1+resin film 2) and the CTE of the resin film 2 (the CTE of the polyimide resin laminated film-the CTE of the resin film 2) is obtained to obtain The change in CTE due to the lamination with the resin film 1.

(8) Determination of chromaticity coordinates

Using a microphotometer (MCPD-2000 manufactured by Otsuka Electronics Co., Ltd.), the transmission chromaticity coordinates (x, y) in the chromaticity diagram of the XYZ color system were measured. In addition, the polyimide resin laminated film on the glass substrate prepared in (1) was used in the measurement. In addition, C light source (x0=0.310, y0=0.316) is used as the light source.

(9) Measurement of surface roughness

Using an atomic force microscope (AFM) (DIMENSION Icon manufactured by BRUKER), perform the peeling surface of the polyimide resin laminate film peeled off by (6) The surface roughness (maximum height (Rz)) of the measurement.

(10) Measurement of 1% weight reduction temperature (heat resistance)

A thermogravimetry device (TGA-50 manufactured by Shimadzu Corporation) was used for the measurement under a nitrogen stream. The heating method is carried out under the following conditions. In the first stage, the temperature is increased to 350°C at a temperature increase rate of 3.5°C/min to remove the adsorbed water of the sample, and in the second stage, it is cooled to room temperature at a temperature decrease rate of 10°C/min. In the third stage, the measurement is performed at a temperature increase rate of 10°C/min to obtain the 1% thermal weight reduction temperature. In addition, the polyimide resin laminated film obtained by laser peeling the polyimide resin laminated film on the glass substrate made by the method described in (6) in (1) was used in the measurement (Examples 1 to 29 ).

(11) Formation of indium tin oxide (ITO) film

The peeling surface of the polyimide resin laminate film peeled from the glass substrate by the method described in (6) was sputtered using a composite oxide target of indium oxide and tin oxide, and an ITO layer with a film thickness of 150 nm To make a film. The pressure at this time was 6.7×10 ^-1 Pa, the substrate temperature was 150 degrees, and a 3 kW DC power supply was used for sputtering.

(12) Measurement of water vapor transmission rate

For the polyimide resin laminated film with ITO film produced by the method described in (11), under the conditions of temperature 40℃, humidity 90%RH, and measuring area 50cm ² , use water vapor transmission rate measurement An apparatus (PERMATRAN (registered trademark) manufactured by MOCON) was used to measure the water vapor transmission rate. The number of samples is set to 2 samples per level, the number of measurements is set to 10 times for the same sample, and the average value is set as the water vapor transmission rate (g/(m ² .day)) as the gas barrier property Evaluation index.

(13) Warpage measurement of glass substrate after resin laminate film formation

The warpage measurement was performed on a 300×350×0.7mm thick glass substrate (manufactured by AN-100 Asahi Glass Co., Ltd.). The polyimide resin laminated film was prepared by the method described in (1), and placed on MITUTOYO (stock). On the precision stone platform (1000mm×1000mm) made by ), at 8 places of each midpoint and each apex of the 4 sides of the test plate, the amount of floating (distance) from the platform was measured with a gap meter. Let the average of these values be the amount of warpage. The measurement is performed at room temperature (25°C).

(14) Evaluation of curling of TFT substrate and color filter substrate

The curling of the TFT substrate and the color filter substrate was evaluated as follows.

The TFT substrate or the color filter substrate peeled from the glass substrate by the method described in (6) was allowed to stand for 30 minutes at room temperature. Cut a 30mm square from the TFT substrate or color filter substrate after static storage, and place it on a smooth glass plate with the substrate side facing downwards, and further stand at room temperature for 30 minutes. Then observe, measure the maximum amount of the place where the 30mm square TFT substrate or the color filter substrate floats from the glass plate as the amount of curl, and evaluate it with the following criteria.

A (very good): The amount of curl is less than 2mm

B (good): The amount of curl is more than 2mm and less than 5mm

C (possible): The amount of curl exceeds 5mm and is less than 10mm

D (bad): The amount of curl exceeds 10 mm or is cylindrical.

(15) Defect evaluation of TFT substrate and color filter substrate

Evaluation of the TFT substrate peeled from the glass substrate by the method described in (6) The number of component defects of the board or pixel defects of the color filter substrate. In the evaluation, an optical microscope (OPTIPHOT 300 manufactured by Nikon Co., Ltd.) was used to visually observe 1,000 elements or pixels.

(Records of used raw materials, etc.)

The abbreviations of the substances used in the examples are summarized below.

PMDA: pyromellitic dianhydride

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

ODPA: 3,3’,4,4’-hydroxydiphthalic dianhydride

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

BSAA: 2,2-bis(4-(3,4-dicarboxyphenoxy)phenyl)propane dianhydride

CBDA: Cyclobutane tetracarboxylic dianhydride

PMDA-HS: 1R, 2S, 4S, 5R-cyclohexane tetracarboxylic dianhydride

BPDA-H: 3,3’,4,4’-Dicyclohexanetetracarboxylic dianhydride

PDA: p-phenylenediamine

3,3’-DDS: 3,3’-diaminodiphenyl sulfide

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

HFHA: structure of chemical formula (3)

BABOHF: structure of chemical formula (5)

BABODS: structure of chemical formula (6)

BABOHA: structure of chemical formula (13)

BABOBA: structure of chemical formula (14)

BAPS: Bis[4-(3-aminophenoxy)phenyl] sulfide

CHDA: trans-1,4-diaminocyclohexane

BABB: structure of chemical formula (15)

DAE: 4,4’-diaminodiphenyl ether

SiDA: Bis(3-aminopropyl)tetramethyldisiloxane

NMP: N-methyl-2-pyrrolidone

GBL: γ-butyrolactone

Synthesis Example 1: Synthesis of polyimide precursor solution

Under a stream of dry nitrogen, 5.0505 g (21.2 mmol) of PMDA, 13.9971 g (23.2 mmol) of HFHA, and 100 g of NMP were added to a 200 mL four-necked flask, and heated and stirred at 65°C. After 6 hours, cool to prepare a polyimide precursor solution.

Synthesis Example 2: Synthesis of polyimide precursor solution

Under a stream of dry nitrogen, 6.2357 g (21.2 mmol) of BPDA, 12.8119 g (21.2 mmol) of HFHA, and 100 g of NMP were added to a 200 mL four-necked flask, and heated and stirred at 65°C. After 6 hours, cool to prepare a polyimide precursor solution.

Synthesis Example 3: Synthesis of polyimide precursor solution

Under a stream of dry nitrogen, 6.4597 g (20.8 mmol) of ODPA, 12.5879 g (20.8 mmol) of HFHA, and 100 g of NMP were added to a 200 mL four-necked flask, and heated and stirred at 65°C. After 6 hours, cool to prepare a polyimide precursor solution.

Synthesis Example 4: Synthesis of polyimide precursor solution

Under a stream of dry nitrogen, 8.0685 g (18.2 mmol) of 6FDA, 10.9792 g (18.2 mmol) of HFHA, and 100 g of NMP were added to a 200 mL four-necked flask, and heated and stirred at 65°C. After 6 hours, cool to prepare a polyimide precursor solution.

Synthesis Example 5: Synthesis of polyimide precursor solution

Under a stream of dry nitrogen, 8.8126 g (16.9 mmol) of BSAA, 10.2350 g (16.9 mmol) of HFHA, and 100 g of NMP were added to a 200 mL four-necked flask, and the mixture was heated and stirred at 65°C. After 6 hours, cool to prepare a polyimide precursor solution.

Synthesis Example 6: Synthesis of polyimide precursor solution

Under a stream of dry nitrogen, 4.6657 g (23.8 mmol) of CBDA, 14.3819 g (23.8 mmol) of HFHA, and 100 g of NMP were added to a 200 mL four-necked flask, and heated and stirred at 65°C. After 6 hours, cool to prepare a polyimide precursor solution.

Synthesis Example 7: Synthesis of polyimide precursor solution

Under a stream of dry nitrogen, 5.1527 g (23.0 mmol) of PMDA-HS, 13.8949 g (23.0 mmol) of HFHA, and 100 g of NMP were added to a 200 mL four-necked flask, and heated and stirred at 65°C. After 6 hours, cool to prepare a polyimide precursor solution.

Synthesis Example 8: Synthesis of polyimide precursor solution

Under a stream of dry nitrogen, 6.4058 g (20.9 mmol) of BPDA-H, 12.6418 g (20.9 mmol) of HFHA, and 100 g of NMP were added to a 200 mL four-necked flask, and heated and stirred at 65°C. After 6 hours, cool to prepare a polyimide precursor solution.

Synthesis Example 9: Synthesis of polyimide precursor solution

Under a stream of dry nitrogen, 5.3869 g (24.0 mmol) of PMDA-HS, 13.6607 g (24.0 mmol) of BABOHF, and 100 g of NMP were added to a 200 mL four-necked flask, and heated and stirred at 65°C. After 6 hours, cool to prepare a polyimide precursor solution.

Synthesis Example 10: Synthesis of polyimide precursor solution

Under a stream of dry nitrogen, 6.0422 g (27.0 mmol) of PMDA-HS, 13.0054 g (27.0 mmol) of BABODS, and 100 g of NMP were added to a 200 mL four-necked flask, and heated and stirred at 65°C. After 6 hours, cool to prepare a polyimide precursor solution.

Synthesis Example 11: Synthesis of polyimide precursor solution

Under a stream of dry nitrogen, 5.2923 g (23.6 mmol) of PMDA-HS, 13.7554 g (23.6 mmol) of BABOHA, and 100 g of NMP were added to a 200 mL four-necked flask, and heated and stirred at 65°C. After 6 hours, cool to prepare a polyimide precursor solution.

Synthesis Example 12: Synthesis of polyimide precursor solution

Under a stream of dry nitrogen, 7.8637 g (26.7 mmol) of BPDA, 11.1840 g (26.7 mmol) of BABOBA, and 100 g of NMP were added to a 200 mL four-necked flask, and heated and stirred at 65°C. After 6 hours, cool to prepare a polyimide precursor solution.

Synthesis Example 13: Synthesis of polyimide precursor solution

Under a stream of dry nitrogen, 6.6445 g (29.6 mmol) of PMDA-HS, 12.4031 g (29.6 mmol) of BABOBA, and 100 g of NMP were added to a 200 mL four-necked flask, and heated and stirred at 65°C. After 6 hours, cool to prepare a polyimide precursor solution.

Synthesis Example 14: Synthesis of polyimide precursor solution

Under a stream of dry nitrogen, 7.9558 g (25.6 mmol) of ODPA, 11.0918 g (25.6 mmol) of BAPS, and 100 g of NMP were added to a 200 mL four-necked flask, and the mixture was heated and stirred at 65°C. After 6 hours, cool to prepare a polyimide precursor solution.

Synthesis Example 15: Synthesis of polyimide precursor solution

Under a stream of dry nitrogen, add 4.7698g (16.2mmol) of BPDA, 1.2114g (5.4mmol) of PMDA-HS, 13.0665g (21.6mmol) of HFHA, and 100g of NMP into a 200mL four-necked flask, and heat and stir at 65°C. . After 6 hours, cool to prepare a polyimide precursor solution.

Synthesis Example 16: Synthesis of polyimide precursor solution

Under a stream of dry nitrogen, add 3.2443g (11.0mmol) of BPDA, 2.4719g (11.0mmol) of PMDA-HS, 13.3314g (22.0mmol) of HFHA, and 100g of NMP into a 200mL four-necked flask, and heat and stir at 65°C. . After 6 hours, cool to prepare a polyimide precursor solution.

Synthesis Example 17: Synthesis of polyimide precursor solution

Under a stream of dry nitrogen, add 1.6557g (5.6mmol) of BPDA, 3.7846g (16.8mmol) of PMDA-HS, 13.6073g (22.5mmol) of HFHA, and 100g of NMP into a 200mL four-necked flask, and heat and stir at 65°C. . After 6 hours, it was cooled to prepare a polyamide acid solution.

Synthesis Example 18: Synthesis of Polyamide Acid Solution

Under a stream of dry nitrogen, 9.0374 g (40.3 mmol) of PMDA-HS, 10.0102 g (40.3 mmol) of 3,3'-DDS, and 100 g of NMP were added to a 200 mL four-necked flask, and heated and stirred at 65°C. After 6 hours, cool to prepare a polyimide precursor solution.

Synthesis Example 19: Synthesis of polyimide precursor solution

Under a stream of dry nitrogen, 14.0776 g (46.0 mmol) of BPDA-H, 4.9700 g (46.0 mmol) of PDA, and 100 g of NMP were added to a 200 mL four-necked flask, and heated and stirred at 65°C. After 6 hours, cool to prepare a polyimide precursor solution.

Synthesis Example 20: Synthesis of polyimide precursor solution

Under a stream of dry nitrogen, 13.7220 g (46.6 mmol) of BPDA, 5.3256 g (46.6 mmol) of CHDA, and 100 g of NMP were added to a 200 mL four-necked flask, and heated and stirred at 65°C. After 6 hours, cool to prepare a polyimide precursor solution.

Synthesis Example 21: Synthesis of polyimide precursor solution

Under a stream of dry nitrogen, 9.3724 g (30.2 mmol) of ODPA, 9.6752 g (30.2 mmol) of TFMB, and 100 g of NMP were added to a 200 mL four-necked flask, and heated and stirred at 65°C. After 6 hours, cool to prepare a polyimide precursor solution.

Synthesis Example 22: Synthesis of polyimide precursor solution

Under a stream of dry nitrogen, 13.9283 g (47.3 mmol) of BPDA, 5.1193 g (47.3 mmol) of PDA, and 100 g of NMP were added to a 200 mL four-necked flask, and heated and stirred at 65°C. After 6 hours, cool to prepare a polyimide precursor solution.

Synthesis Example 23: Synthesis of polyimide precursor solution

Under a stream of dry nitrogen, 7.3799 g (25.1 mmol) of BPDA, 11.4074 g (25.1 mmol) of BABB, and 100 g of NMP were added to a 200 mL four-necked flask, and heated and stirred at 65°C. After 6 hours, cool to prepare a polyimide precursor solution.

Preparation example 1: Adjustment of polyimide precursor/silica nanoparticle solution

The organosilica was added to the polyimide precursor solution obtained in Synthesis Example 2 in such a way that 100 parts by weight of the polyimide precursor and the silica particles became 100 parts by weight in the polyimide precursor solution obtained in Synthesis Example 2. Sol (manufactured by Nissan Chemical Industry Co., Ltd., trade name PMA-ST, particle size 10-30nm) to obtain a polyimide precursor-silica nanoparticle varnish.

Preparation example 2: Adjustment of polyimide precursor/silica nanoparticle solution

In the polyimide precursor solution obtained in Synthesis Example 22, 100 parts by weight of the polyimide precursor and 50 parts by weight of the silica particles were added to the polyimide precursor solution. Sol (manufactured by Nissan Chemical Industry Co., Ltd., trade name PMA-ST, particle size 10-30nm) to obtain a polyimide precursor-silica nanoparticle varnish.

Using the polyimide precursor solution of each synthesis example and preparation example, a polyimide resin film was prepared by the method described in (2), and the laser releasability was evaluated by the method described in (6). The maximum absorbance of the diamine solution in the wavelength range of 300~400nm, the absorbance at wavelengths of 266nm, 308nm, 343nm, 351nm, 355nm, and the CTE of the polyimide resin film are combined. Table 1 shows the results.

Example 1

Using the method described in (1), using the polyimide precursor solutions of Synthesis Example 1 and Synthesis Example 20, a resin film 1 with a thickness of 1 μm (fired at 300°C) and a resin film 2 with a thickness of 10 μm (300°C) were produced. Roasting). Using the obtained polyimide resin laminated film, the light transmittance of the resin laminated film, the laser peel test, and the CTE were measured by the methods described in (3), (6)~(10) and (12). Measurement, measurement of Tg, measurement of CTE change due to layering, measurement of chromaticity coordinates, measurement of Rz of peeling surface, measurement of 1% weight loss temperature, water vapor after forming of ITO film on peeling surface Measurement of penetration rate. The results are shown in Table 2. In addition, the minimum value of the light transmittance of the resin film 1 in the wavelength range of 300 to 400 nm in the wavelength range of 300 to 400 nm, and the minimum value of the light transmittance in the wavelength range of 266 nm, 308 nm, 343 nm, Light transmittance at 351nm and 355nm. Table 6 shows the results.

Examples 2~11

Except having changed the polyimide precursor solution used in the preparation of the resin film 1 as described in Tables 2 to 3, it carried out similarly to Example 1, and produced the polyimide resin laminated film. In the same manner as in Example 1, the measurement of light transmittance, laser peeling test, CTE measurement, Tg measurement, CTE change measurement due to layering, chromaticity coordinate measurement, and Rz measurement of the peeled surface were performed. , Measurement of 1% weight loss temperature, measurement of water vapor transmission rate of ITO film on the peeling surface after forming. The results are shown in Tables 2 to 3. In addition, Table 6 shows the minimum light transmittance of the resin film 1 in the wavelength range of 300 to 400 nm when it is made into a film with a thickness of 100 nm, and at the wavelengths of 266 nm, 308 nm, 343 nm, 351 nm, 355 nm 的光 Transmittance.

Example 12

Except that the polyimide resin precursor solution of Synthesis Example 12 was used in the production of the resin film 1, and the firing temperature was changed to 400°C, the same procedure as in Example 1 was carried out to produce a polyimide resin laminated film. In the same manner as in Example 1, the measurement of light transmittance, laser peeling test, CTE measurement, Tg measurement, CTE change measurement due to layering, chromaticity coordinate measurement, and Rz measurement of the peeled surface were performed. , Measurement of 1% weight loss temperature, measurement of water vapor transmission rate of ITO film on the peeling surface after forming. Table 3 shows the results. In addition, Table 6 shows the minimum light transmittance of the resin film 1 in the wavelength range of 300 to 400 nm and the light transmittances at wavelengths of 266 nm, 308 nm, 343 nm, 351 nm, and 355 nm when used as a film with a thickness of 100 nm.

Examples 13~17

Except that the polyimide precursor solution used in the production of the resin film 1 was changed as described in Table 3, the same procedure as in Example 1 was carried out to produce a polyimide resin laminated film. In the same manner as in Example 1, the measurement of light transmittance, laser peeling test, CTE measurement, Tg measurement, CTE change measurement due to layering, chromaticity coordinate measurement, and Rz measurement of the peeled surface were performed. , Measurement of 1% weight loss temperature, measurement of water vapor transmission rate of ITO film on the peeling surface after forming. Table 3 shows the results. In addition, Table 6 shows the minimum light transmittance of the resin film 1 in the wavelength range of 300 to 400 nm and the light transmittances at wavelengths of 266 nm, 308 nm, 343 nm, 351 nm, and 355 nm when used as a film with a thickness of 100 nm.

Examples 18-22

Except that the polyimide precursor solution of Synthesis Example 7 was used instead of the polyimide precursor solution of Synthesis Example 1, and the film thickness of the resin film 1 was changed as described in Table 4, the same procedure as in Example 1 was carried out to produce polyimide Laminated film of imide resin. In the same manner as in Example 1, the measurement of light transmittance, laser peeling test, CTE measurement, CTE change due to layering, Tg measurement, chromaticity coordinate measurement, and peeling surface Rz measurement were performed. , Measurement of 1% weight loss temperature, measurement of water vapor transmission rate of ITO film on the peeling surface after forming. Table 4 shows the results. In addition, Table 6 shows the minimum light transmittance of the resin film 1 in the wavelength range of 300 to 400 nm and the light transmittances at wavelengths of 266 nm, 308 nm, 343 nm, 351 nm, and 355 nm when used as a film with a thickness of 100 nm.

Examples 23~25

Except that the polyimide precursor solution described in Table 4 was used in the production of resin film 1, and the polyimide precursor solution described in Table 4 was used in the production of resin film 2, and its calcination temperature was set to Except for 400°C, the same procedure as in Example 1 was carried out to produce a polyimide resin laminated film. In the same manner as in Example 1, the measurement of light transmittance, laser peeling test, CTE measurement, Tg measurement, CTE change measurement due to layering, chromaticity coordinate measurement, and Rz measurement of the peeled surface were performed. , Measurement of 1% weight loss temperature, measurement of water vapor transmission rate of ITO film on the peeling surface after forming. Table 4 shows the results. In addition, Table 6 shows the minimum light transmittance of the resin film 1 in the wavelength range of 300 to 400 nm and the light transmittances at wavelengths of 266 nm, 308 nm, 343 nm, 351 nm, and 355 nm when used as a film with a thickness of 100 nm.

Examples 26-27

Except that the polyimide precursor solution described in Table 4 was used in the production of the resin film 1 and the firing temperature was changed to 400°C, and the polyimide precursor of Synthesis Example 22 was used in the production of the resin film 2. Except that the baking temperature of the solution was set to 400°C, the same procedure as in Example 1 was carried out to produce a polyimide resin laminated film. In the same manner as in Example 1, the measurement of light transmittance, laser peeling test, CTE measurement, Tg measurement, CTE change measurement due to layering, chromaticity coordinate measurement, and Rz measurement of the peeled surface were performed. , Measurement of 1% weight loss temperature, measurement of water vapor transmission rate of ITO film on the peeling surface after forming. Table 4 shows the results. In addition, Table 6 shows the minimum light transmittance of the resin film 1 in the wavelength range of 300 to 400 nm and the light transmittances at wavelengths of 266 nm, 308 nm, 343 nm, 351 nm, and 355 nm when used as a film with a thickness of 100 nm.

Examples 28~29

Except having used the polyimide precursor solution described in Table 4 in the production of the resin film 2, the same procedure as in Example 23 was carried out to produce a polyimide resin laminated film. In the same manner as in Example 1, the measurement of light transmittance, laser peeling test, CTE measurement, Tg measurement, CTE change measurement due to layering, chromaticity coordinate measurement, and Rz measurement of the peeled surface were performed. , Measurement of 1% weight loss temperature, measurement of water vapor transmission rate of ITO film on the peeling surface after forming. Table 4 shows the results. In addition, Table 6 shows the minimum light transmittance of the resin film 1 in the wavelength range of 300 to 400 nm and the light transmittances at wavelengths of 266 nm, 308 nm, 343 nm, 351 nm, and 355 nm when used as a film with a thickness of 100 nm.

Comparative example 1~2

Except that the polyimide precursor solution used in the production of the resin film 1 was changed as described in Table 5, the same procedure as in Example 1 was carried out to produce a polyimide resin laminated film. In the same manner as in Example 1, the measurement of the light transmittance, the laser peel test, and the measurement of the chromaticity coordinates were performed. Table 5 shows the results. ^{Even with the maximum irradiation energy (400mJ/cm 2} ) of the device used in the laser peel test, the resin laminate film cannot be peeled off. Therefore, the measurement of CTE, the measurement of the change in CTE due to layering, the measurement of the Rz of the peeling surface, the measurement of the 1% weight loss temperature, the formation of the ITO film, and the measurement of the water vapor transmission rate are not implemented. In addition, Table 6 shows the minimum light transmittance of the resin film 1 in the wavelength range of 300 to 400 nm and the light transmittances at wavelengths of 266 nm, 308 nm, 343 nm, 351 nm, and 355 nm when used as a film with a thickness of 100 nm.

Comparative example 3

Except that the polyimide precursor solution used in the production of the resin film 1 was changed as described in Table 5, the same procedure as in Example 24 was carried out to produce a polyimide resin laminated film. In the same manner as in Example 1, the measurement of the light transmittance, the laser peel test, and the measurement of the chromaticity coordinates were performed. Table 5 shows the results. ^{Even with the maximum irradiation energy (400mJ/cm 2} ) of the device used in the laser peel test, the resin laminate film cannot be peeled off. Therefore, the measurement of CTE, the measurement of the change in CTE due to layering, the measurement of the Rz of the peeling surface, the measurement of the 1% weight loss temperature, the formation of the ITO film, and the measurement of the water vapor transmission rate are not implemented. In addition, Table 6 shows the minimum light transmittance of the resin film 1 in the wavelength range of 300 to 400 nm and the light transmittances at wavelengths of 266 nm, 308 nm, 343 nm, 351 nm, and 355 nm when used as a film with a thickness of 100 nm.

Adjustment example 3: Synthesis of polyamide acid solution

DAE (0.30 mol), PDA (0.65 mol) and SiDA (0.05 mol) were added together with 850 g of GBL and 850 g of NMP, ODPA (0.9975 mol) was added, and the reaction was carried out at 80° C. for 3 hours. Add maleic anhydride (0.02mol), further The reaction was carried out at 80°C for 1 hour to obtain a polyamide acid solution (resin concentration 20% by weight).

Preparation example 4; production of black resin composition for forming black matrix

In 250g of the polyamide acid solution of adjustment example 3, 50g of carbon black (MA100 manufactured by Mitsubishi Chemical Corporation) and 200g of NMP were mixed, Dyno-Mill KDL-A was used, and zirconia beads with a diameter of 0.3 mm were used to Dispersion treatment was performed at 3200 rpm for 3 hours to obtain a black resin dispersion.

To 50 g of this black dispersion liquid, 49.9 g of NMP and 0.1 g of a surfactant (manufactured by LC951 Kubumoto Chemical Co., Ltd.) were added to obtain a non-photosensitive black resin composition.

Modulation example 5: Production of photosensitive color photoresist

8.05 g of Pigment Red PR177 and 50 g of 3-methyl-3-methoxybutanol were added together, and after dispersing at 7000 rpm for 5 hours using a homogenizer, the glass beads were filtered and removed. 134.75 g of a photosensitive acrylic resin solution (AC) with a concentration of 20% by weight was added to obtain a photosensitive red resist. The photosensitive acrylic resin solution (AC) is based on 70.00g of acrylic copolymer solution (DAICEL Chemical Industry Co., Ltd. "Cyclomer" P, ACA-250, 43wt% solution), 30.00g of neopentyl as a multifunctional monomer To tetraol tetramethacrylate, 15.00 g of "Irgacure" 369 as a photopolymerization initiator, 260.00 g of cyclopentanone was added. In the same way, a photosensitive green resist composed of pigment green PG38 and pigment yellow PY138, and a photosensitive blue resist composed of pigment blue PB15:6 were obtained.

Example 30 Fabrication of Color Filter (Figure 1)

[1] Production of polyimide resin laminated film

Except that a 300mm×350mm×0.7mm thick glass substrate (manufactured by AN100 Asahi Glass Co., Ltd.) was used as the supporting substrate (symbol: 1), and the firing temperature of the polyimide resin film A was set to 300°C, the same as in Example 18 In the same manner, a resin laminated film (symbol: 2) of a polyimide resin laminated film composed of a polyimide laminated film A (symbol: 2A) and a resin film (symbol: 2B) was produced.

[2] Production of resin black matrix

The black resin composition prepared in Adjustment Example 4 was spin-coated on the polyimide resin laminated film on the glass substrate prepared above, and dried with a hot plate at 130° C. for 10 minutes to form a black resin coating film. Spin-coated positive photoresist (manufactured by SHIPLEY, "SRC-100"), pre-baked at 120°C for 5 minutes with a hot plate, using an ultra-high pressure mercury lamp, irradiating 100mJ/cm ^{2 of} ultraviolet rays, and masking exposure, using 2.38 % Tetramethylammonium hydroxide aqueous solution, the photoresist is developed and the black resin coating is etched at the same time, the pattern is formed, the photoresist is peeled off with methyl cellosolve acetate, and heated at 280℃ for 10 Minutes to imidize the polyimide resin to form a black matrix in which carbon black is dispersed in the polyimide resin (symbol: 3). The thickness of the black matrix was measured and the result was 1.4 μm.

[3] The production of colored layers

Adjust the spin coating on the polyimide resin laminate film on the patterned glass substrate of the black matrix produced in [1] and [2] so that the film thickness at the opening of the black matrix after heat treatment becomes 2.0 μm The number of revolutions of the machine was coated with the photosensitive red photoresist adjusted in Preparation Example 5, and the red colored layer was obtained by pre-baking the hot plate at 100°C for 10 minutes. Next, using a CANON (stock) ultraviolet exposure machine "PLA-5011", for the openings of the black matrix and a part of the black matrix, a chrome mask through which light penetrates in an island shape is used, and 100mJ/cm ² (365nm The intensity of ultraviolet light) exposure. After exposure, it was developed by immersing it in a developer solution composed of 0.2% tetramethylammonium hydroxide aqueous solution. After washing with pure water, it was heated in an oven at 230°C for 30 minutes to produce a red coloration. Pixel (symbol: 4R). In the same way, the green coloring pixel composed of photosensitive green photoresist (symbol: 4G) and the blue coloring pixel composed of photosensitive blue photoresist (symbol: 4B) adjusted in Preparation Example 5 were produced. A polyimide substrate color filter made on a glass substrate (Figure 1).

Examples 31 to 33, Comparative Example 4

Except that the production of the polyimide resin laminated film was not set to the same conditions as in Example 18, but was changed to the same conditions as in the example described in Table 6, the same procedure as in Example 30 was carried out to produce a color Filter.

For the color filters of the respective examples and comparative examples, the laser peel test was carried out by the method described in (6), and the curling of the color filter was evaluated by the method described in (14), and the curl of the color filter was evaluated in (15) The method of recording is used to evaluate the pixel defect. In addition, in each of the Examples and Comparative Examples, after the polyimide resin laminated film was produced on the glass substrate as the supporting substrate, the amount of warpage of the glass substrate was measured by the method described in (13). The results are shown in Table 7.

In Examples 30 to 33, there is no particular problem of rejection or color mixing, and good color filters can be obtained. However, compared with the color filter of Example 30, in the color filters of Examples 31 to 33, the curl is large, and the pixel defect is also increased. It is believed that the reason for this is the increase in the CTE of the polyimide resin laminate film. In Comparative Example 4, the color filter could not be peeled off from the glass substrate.

Example 34 Fabrication of TFT substrate (Figure 2)

[1] Production of polyimide resin laminated film

Except that a 300mm×400mm×0.7mm thick glass substrate (AN100 (Asahi Glass Co., Ltd.)) was used as the supporting substrate (symbol: 1), and the firing temperature of the polyimide resin film A was set to 300°C, the same as in Example 26 In the same manner, a resin laminated film (symbol: 2') of a polyimide resin laminated film composed of a polyimide resin film A (symbol: 2A') and a resin film (symbol: 2B') was produced.

[2] Production of TFT substrate

On the polyimide resin laminated film (on a glass substrate) produced by the above method, a gas barrier layer (symbol: 5) composed of SiO was formed by using a plasma CVD method. Then, a bottom gate type TFT (symbol: 6) is formed to cover the TFT, and an insulating film (not shown) _{composed of Si 3} N _{4 is formed.} Next, after forming a contact hole in the insulating film, a wiring (height 1.0 μm, not shown) connected to the TFT through the contact hole is formed on the insulating film. This wiring is used to connect organic EL elements and TFTs formed between TFTs or in a later step.

Furthermore, in order to flatten the unevenness caused by the wiring formation, a flattening layer (symbol: 7) is formed on the insulating film in a state where the unevenness caused by the wiring is buried. The flattening layer is formed by spin-coating photosensitive polyimide varnish on the substrate, pre-baking on a hot plate (120℃×3 minutes), and then exposing and developing through the mask of the desired pattern. It is performed by heat treatment at 230°C for 60 minutes under air flow. The coatability when applying the varnish is good. After exposure, development, and heat treatment, no wrinkles or cracks can be seen in the resulting flattened layer. Furthermore, the level of wiring The average step difference is 500 nm, and a 5 μm square contact hole is formed in the produced planarization layer with a thickness of about 2 μm.

Examples 35~36

Except that the production of the polyimide resin laminate film was not set to the same conditions as in Example 26, but was changed to the same conditions as in the examples described in Table 8, the same procedures as in Example 34 were carried out to produce TFTs. Substrate.

For the obtained TFT substrate (Figure 2), the laser peel test was performed by the method described in (6), the curl of the TFT substrate was evaluated by the method described in (14), and the method described in (15) was performed Evaluation of component defects. In addition, after the polyimide laminated film was produced on the glass substrate, the amount of warpage of the glass substrate was measured by the method described in (13). The results are shown in Table 8.

Example 37 Production of organic EL display with polyimide substrate (Figure 3)

[1] Production of polyimide resin laminated film

Using the method described in Example 34, a resin laminated film (symbol: :2').

[2] Production of TFT substrate

According to the method described in Example 34, a TFT substrate was produced.

[3] Production of top emission organic EL devices

On the planarization layer (symbol: 7) of the TFT obtained by the above method, the following parts were formed to fabricate a top emission type organic EL device. First, on the planarization layer (symbol: 7), the first electrode (symbol: 8) composed of Al/ITO (Al: reflective electrode) is formed by connecting to the wiring through the contact hole. Then, the photoresist is coated, pre-baked, exposed through the mask of the desired pattern, and developed. Using this photoresist pattern as a mask, pattern processing of the first electrode (symbol: 8) is performed by wet etching using ITO etching. Then, a photoresist stripping solution (a mixture of monoethanolamine and diethylene glycol monobutyl ether) is used to strip the photoresist pattern. The peeled substrate was washed with water, and heated and dehydrated at 200° C. for 30 minutes to obtain an electrode substrate with a planarization layer. The thickness change of the planarization layer is less than 1% after heating and dehydrating compared to before the peeling liquid treatment. The first electrode (symbol: 8) thus obtained corresponds to the anode of the organic EL device.

Next, an insulating layer (symbol: 9) covering the end of the first electrode (symbol: 8) is formed. In the insulating layer, the same photosensitive polyimide varnish is used. By providing this insulating layer, a short circuit between the first electrode and the second electrode (symbol: 10) formed in the subsequent steps can be prevented.

Furthermore, through the desired pattern mask in the vacuum evaporation device, a hole transport layer, an organic light-emitting layer, and an electron transport layer are vapor-deposited in order, and a red organic EL light-emitting layer (symbol: 11R) and a green organic EL light-emitting layer are installed. Layer (symbol: 11G), blue organic EL light-emitting layer (symbol: 11B). Next, on the entire surface above the substrate, a second electrode (symbol: 10) composed of Mg/ITO is formed. Furthermore, the SiON sealing film is formed by CVD film formation (symbol No.: 12).

Next, by the method described in (6), the organic EL element was peeled from the glass substrate to produce an organic EL display (Fig. 3). To the obtained active matrix organic EL display, voltage was applied through the driving circuit, and the result showed good light emission. In addition, the obtained organic EL device is not inferior in comparison with the organic EL device produced using the glass substrate.

Example 38 Production of organic EL display with polyimide substrate (Figure 4)

[1] Production of polyimide resin laminated film

Using the method described in Example 34, a resin laminated film (symbol: :2').

[2] Production of TFT substrate

According to the method described in Example 34, a TFT substrate was produced.

[3] Production of top emission organic EL devices

Except for changing the organic light-emitting layer to a white organic EL light-emitting layer (symbol: 11W), a top emission type organic EL element was produced by the method described in Example 34.

[4] Production of organic EL display

The glass substrate-attached color filter obtained in Example 30 and the glass substrate-attached top emission organic EL device obtained in [3] above were bonded via an adhesive layer (symbol: 13). Next, by the method described in (6), the color filter and the organic EL element were peeled off from the glass substrate to produce an organic EL display (Fig. 4). To the obtained active matrix organic EL display, voltage was applied through the driving circuit, and the result showed good light emission. Also, with In comparison with organic EL devices made with glass substrates, the obtained organic EL devices are not inferior.

Claims (20)

A resin laminated film, which is a resin laminated film having a polyimide resin film on at least one surface of the resin film, the polyimide resin film is the following polyimide resin film A, and the polyimide resin film The main component of the diamine residue in the polyimide contained in the amine resin film A is derived from the following (B) diamine derivative; the polyimide resin film A: when it is made into a film with a thickness of 100nm, In the wavelength range of 300~400nm, the minimum light transmittance is less than 50% of the polyimide resin film; (B) Diamine derivative: contains the structure shown in formula (1) or (2), and is made When it is a N-methyl-2-pyrrolidone solution with a concentration of 1×10 ^-4 mol/L, the maximum absorbance in the wavelength range of 300~400nm under the condition of the optical path length of 1cm exceeds 0.6 Diamine derivatives,

In the formulas (1)~(2), A represents a single bond, an oxygen atom, a sulfur atom, a sulfonyl group, a phenyl group, a stilbene group, a divalent organic group of 1 to 5 carbon atoms in which the hydrogen atom can be substituted by a halogen atom, Or a divalent organic group formed by connecting two or more of them, R ¹ to R ⁴ each independently represents a monovalent organic group with 1 to 10 carbon atoms having at least one amine group. The resin laminated film of claim 1, wherein the maximum value of the absorbance of the (B) diamine derivative is 1.0 or more. The resin laminated film of claim 1 or 2, wherein the thickness of the polyimide resin film is 100 nm to 1 μm. The resin laminate film of claim 1 or 2, wherein the acid dianhydride residues in the polyimine contained in the polyimide resin film A have aromatic acid dianhydride residues as the main component. The resin laminated film of claim 4, wherein the aromatic acid dianhydride residue is derived from pyromellitic dianhydride or 3,3',4,4'-biphenyltetracarboxylic dianhydride. The resin laminated film of claim 1 or 2, wherein the acid dianhydride residues in the polyimide contained in the polyimide resin film A are mainly composed of alicyclic acid dianhydride residues, or The aliphatic acid dianhydride residue is used as the main component, or the total of the alicyclic acid dianhydride residue and the aliphatic acid dianhydride residue is used as the main component. The resin laminated film of claim 6, wherein the acid dianhydride residues in the polyimine contained in the polyimide resin film A are mainly composed of alicyclic acid dianhydride residues, or are The total of cyclic acid dianhydride residues and aliphatic acid dianhydride residues is the main component, and the alicyclic acid dianhydride residue is derived from a tetracarboxylic acid represented by any one of formulas (3) to (6) Dianhydride compounds,

Such as the resin laminated film of claim 1 or 2, wherein the linear thermal expansion coefficient of the resin laminated film is -10~ in the range of 50℃~200℃ Below 30ppm/℃. The resin laminated film of claim 1 or 2, wherein the glass transition temperature of the resin laminated film is 400°C or higher. The resin laminate film of claim 1 or 2, wherein the number of laminate layers of the resin laminate film is 2. The resin laminated film of claim 1 or 2, wherein among the resin laminated film, the resin film other than the polyimide resin film contains a resin film selected from the group consisting of polyimide resin, polybenzo

At least one type of resin from the group of azole resin, polyamide resin, and polyamide resin. A laminated body provided with a support substrate on the polyimide resin film A of the resin laminated film according to any one of claims 1 to 11. A TFT substrate provided with a TFT on the resin laminated film according to any one of claims 1 to 11. An organic EL element provided with an organic EL element on a resin laminate film as in any one of claims 1 to 11. A color filter, which is provided with a color filter on the resin laminate film of any one of claims 1 to 11. A method for manufacturing a resin laminate film, which at least includes the following steps (1) to (3): (1) on a supporting substrate, the steps of manufacturing the following polyimide resin film A; (2) on the resin The step of further laminating a resin film on the film to form a resin laminate film; (3) the step of irradiating ultraviolet light from the side of the supporting substrate to peel off the resin laminate film, Polyimide resin film A: When made into a film with a thickness of 100nm, in the wavelength range of 300~400nm, the minimum light transmittance is less than 50% of the polyimide resin film. The method for manufacturing a resin laminated film according to claim 16, wherein the firing temperature of the resin film used in at least one of the steps (1) or (2) is 400°C or higher. A method for manufacturing a TFT substrate, which at least includes the following steps (1) to (4): (1) on a support substrate, the steps of manufacturing the following polyimide resin film A; (2) on the resin film The step of further laminating a resin film to form a resin laminate film; (3) a step of forming a TFT on the resin laminate film; (4) a step of irradiating ultraviolet light from the side of the supporting substrate to peel off the resin laminate film, polyimide Resin film A: When made into a film with a thickness of 100nm, a polyimide resin film with a minimum light transmittance of less than 50% in the wavelength range of 300~400nm. A method of manufacturing an organic EL device, which at least includes the following steps (1) to (4): (1) on a supporting substrate, the steps of manufacturing the following polyimide resin film A; (2) on the resin The step of further laminating a resin film on the film to form a resin laminate film; (3) the step of forming an organic EL element on the resin laminate film; (4) The step of irradiating ultraviolet light from the side of the supporting substrate to peel off the resin laminate film. Polyimide resin film A: When made into a film with a thickness of 100nm, the light transmittance is the smallest in the wavelength range of 300~400nm. Polyimide resin film with a value less than 50%. A method for manufacturing a color filter, which at least includes the following steps (1) to (5): (1) on a supporting substrate, manufacturing the following polyimide resin film A pair of steps; (2) in the The step of further laminating a resin film on the resin film to form a resin laminate film; (3) the step of forming a black matrix on the resin laminate film; (4) the step of forming colored pixels on the resin laminate film; (5) from The step of irradiating the support substrate with ultraviolet light and peeling off the resin laminate film. Polyimide resin film A: When made into a film with a thickness of 100nm, in the wavelength range of 300~400nm, the minimum light transmittance is less than 50% The polyimide resin film.

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