JP6405616B2 - LAMINATE MANUFACTURING METHOD, LAMINATE, DEVICE LAMINATE, AND DEVICE FILM - Google Patents

Description

  The present invention relates to a method for producing a laminate used for making a flexible device and the like, and relates to a method for producing a laminate excellent in peelability between a carrier substrate and a polyimide film.

  Currently, glass substrates are mainly used in the field of display devices such as liquid crystal displays, organic EL displays and electronic paper, the field of light receiving devices such as solar cells, and the field of light emitting devices such as organic EL lighting. In these device fields, weight reduction and thinning are required, but there is a problem that when the glass substrate is reduced in weight and thickness, the strength is lowered and the glass substrate is easily broken.

Therefore, a plastic film substrate has attracted attention as an alternative to a glass substrate generally used in various devices.
Commonly used plastic film substrates include PEN (polyethylene naphthalate resin), PES (polyether sulfone resin), PET (polyethylene terephthalate resin), BCB (benzocyclobutene resin), and the like. . However, these substrates have problems such as low heat resistance and complicated film forming process.

On the other hand, polyimide films are attracting attention as substrates for flexible devices such as displays, organic EL or photoelectric conversion elements because they are excellent in heat resistance, have little change in physical properties over a wide temperature range, and are tough.
When manufacturing a device with a circuit formed on a plastic film substrate, the plastic film is formed on the carrier substrate, and after the circuit is formed on the plastic film, the plastic film with the circuit formed is easily peeled from the carrier substrate. It is preferable that the cost can be reduced by simplifying the process.
For example, Patent Document 1 discloses a step of forming a film by coating and forming a polyamic acid resin solution on a carrier substrate, a step of forming a circuit on the film, and a device film having a circuit formed on the surface of the carrier. A method for obtaining a flexible device by a process of peeling from a substrate is described.

  Patent Document 2 describes a method for producing a laminate having a smooth peeling by superposing an inorganic layer having a silane coupling layer and a polyimide film, and heating and pressurizing both.

JP 2010-202729 A JP 2011-11455 A

However, according to the study of the inventors of the present application, it has been found that the method described in Patent Document 1 allows the polyimide film layer to adhere firmly to the carrier substrate when glass is used for the carrier substrate, for example. This is presumably because the glass and the polyimide film form a strong intermolecular interaction.
If a strong force is applied to peel the strongly adhered polyimide film layer from the carrier substrate, the polyimide film layer may be deteriorated such as warpage. Furthermore, the circuit on the polyimide film layer is also damaged, and the production efficiency may be lowered, or the performance of the flexible device may be lowered.

  In addition, as a method of peeling the polyimide film layer from the carrier substrate, a method of immersing the carrier substrate having the polyimide film in water and a method of irradiating the polyimide film layer with a laser are also used. However, even by such a method, not only the polyimide film absorbs water or deteriorates, but also the circuit on the polyimide film may be damaged, which makes it difficult to use as a device.

On the other hand, a method for producing a laminate by heating a molded polyimide film as in Patent Document 2 to a carrier substrate such as an inorganic layer and applying pressure or the like is directly applied to the carrier substrate in a liquid composition. When the manufacturing method of the laminated body which applies a thing and heat-drys and creates a polyimide film layer is compared, the number of manufacturing processes will increase, and the film will be bent at the time of attachment, resulting in a significant decrease in yield. There is a problem.
Further, in the former method, a film created in a separate process is brought in from the outside, so that a problem that foreign matters such as dust and dust that should not be attached to the film are brought into the device manufacturing process easily occurs.
Foreign matter brought into the device manufacturing process enters between them when sticking the polyimide film to the carrier substrate, resulting in foreign matter defects in the laminate or device, which greatly reduces the product yield. It is conceivable that

An object of this invention is to provide the method of manufacturing the laminated body which becomes easy to peel the polyimide film layer obtained by apply | coating and drying a solution from a carrier substrate, and can improve a production yield.
It is another object of the present invention to provide a laminate having high transparency and durability against ultraviolet rays and capable of easily peeling the carrier substrate and the polyimide film layer contained in the laminate.

  In view of the above circumstances, the present inventors have intensively studied a method for easily and efficiently peeling a device film having a circuit formed on a polyimide film layer from a carrier substrate. As a result, the object of the present invention is achieved by applying and drying a polyamic acid resin solution and / or a polyimide resin solution on a carrier substrate surface-treated with a silane coupling agent having a specific structure, thereby forming a polyimide film layer. As a result, the present invention has been completed.

The present invention relates to the following items.
[1] A method for producing a laminate comprising a carrier substrate, a silane coupling layer and a polyimide film layer,
Providing a silane coupling layer on the carrier substrate surface;
A step of applying a polyamic acid resin solution and / or a polyimide resin solution on the silane coupling layer and providing a polyimide film layer by drying.
[2] The method for producing a laminate according to [1], wherein the step of providing the silane coupling layer uses at least one silane coupling agent selected from the following general formulas (1) to (3). .

(In general formula (1),
A ^{1 to} A ⁴ each independently represents an organic group that does not contain an epoxy group and an amino group,
At least one of A ^{1 to} A ⁴ represents an alkoxy group which may have a substituent, an acyloxy group which may have a substituent, or a halogen atom. )

(In General Formula (2), A ^{5 to} A ⁷ each independently have an alkyl group which may have a substituent, an acyl group which may have a substituent, or a substituent. The alkyl group, the acyl group, and the substituent that the aromatic group may have does not include an epoxy group and an amino group, and Y ¹ does not include an epoxy group and an amino group, An organic group, m ¹ represents an integer of 2 or more, and a plurality of Y ¹ and A ⁷ present in one molecule of the silane coupling agent represented by the general formula (2) may be the same or different. .)

(In General Formula (3), A ^{8 to} A ¹³ each independently have an alkyl group which may have a substituent, an alkoxy group which may have a substituent, or a substituent. An acyloxy group which may be present, and the substituent which the alkyl group, alkoxy group and acyloxy group may have does not include an epoxy group and an amino group,
X ¹ represents a —NH— group or a group represented by the following general formula (4).

(In General Formula (4), R ¹ and R ² each independently represents an alkyl group which may have a substituent, and the substituent which the alkyl group may have includes an epoxy group and an amino group. No group is included, and m ² represents an integer of 1 or more.)
[3] The method for producing a laminate according to [1] or [2], wherein the polyimide film layer includes a structure represented by the following general formula (8).

[In general formula (8), R ³ represents a tetravalent organic group,
R ⁴ represents a divalent organic group,
n represents an integer of 1 or more, and when n is 2 or more, a plurality of R ³ and R ⁴ present in one molecule of the structure represented by the general formula (8) may be the same or different. . ]
[4] The method for producing a laminate according to [3], wherein R ^{4 in the} general formula (8) is represented by the following general formula (10).

(In General Formula (10), Ring A ²⁰ and Ring A ²¹ are each independently an alicyclic hydrocarbon group which may have a substituent, or an aromatic group which may have a substituent. Indicate
p and q each independently represent an integer of 0 or more and 10 or less. However, neither p nor q is 0.
X ⁴ is a direct bond, an oxygen atom, a sulfur atom, an alkylene group which may have a substituent, a sulfonyl group, a sulfinyl group, a sulfide group, a carbonyl group, an aromatic group which may have a substituent,- NH-C (= O) - group or an -NH- group, or _{-O-C z} H 2z -O- group, z is an integer of 1 to 5.
Y ¹⁰ and Y ¹¹ each independently represent a direct bond, an oxygen atom, a sulfur atom, an alkylene group which may have a substituent, a sulfonyl group, a sulfinyl group, a sulfide group, or a carbonyl group. When p and / or q is 2 or more, the plurality of Y ¹⁰ , Y ¹¹ , ring A ²⁰ and ring A ²¹ may be different from each other. )
[5] The above general formula (8), wherein the general formula (8) is represented by the following general formula (9):
[4] The method for producing a laminate according to [4].

[In general formula (9), R ⁵ represents a divalent organic group,
a represents an integer of 1 or more, and when a is 2 or more, a plurality of R ⁵ present in one molecule of the structure represented by the general formula (9) may be the same or different. ]
[6] A laminate having a silane coupling layer between the carrier substrate and the polyimide film layer, wherein the silane coupling layer is derived from the silane coupling agent represented by the general formulas (1) to (3) And a polyimide film layer having a structure represented by the general formula (8).

(In general formula (1),
A ^{1 to} A ⁴ each independently represents an organic group that does not contain an epoxy group and an amino group,
At least one of A ^{1 to} A ⁴ represents an alkoxy group which may have a substituent, an acyloxy group which may have a substituent, or a halogen atom. )

(In General Formula (2), A ^{5 to} A ⁷ each independently have an alkyl group which may have a substituent, an acyl group which may have a substituent, or a substituent. The alkyl group, the acyl group, and the substituent that the aromatic group may have does not include an epoxy group and an amino group, and Y ¹ does not include an epoxy group and an amino group, An organic group, m ¹ represents an integer of 2 or more, and a plurality of Y ¹ and A ⁷ present in one molecule of the silane coupling agent represented by the general formula (2) may be the same or different. .)

(In General Formula (3), A ^{8 to} A ¹³ each independently have an alkyl group which may have a substituent, an alkoxy group which may have a substituent, or a substituent. An acyloxy group which may be present, and the substituent which the alkyl group, alkoxy group and acyloxy group may have does not include an epoxy group and an amino group,
X ¹ represents a —NH— group or a group represented by the following general formula (4).

(In General Formula (4), R ¹ and R ² each independently represents an alkyl group which may have a substituent, and the substituent which the alkyl group may have includes an epoxy group and an amino group. No group is included, and m ² represents an integer of 1 or more.)

[In general formula (8), R ³ represents a tetravalent organic group,
R ⁴ represents a divalent organic group,
n represents an integer of 1 or more, and when n is 2 or more, a plurality of R ³ and R ⁴ present in one molecule of the structure represented by the general formula (8) may be the same or different. . ]
[7] A device laminate comprising a device formed on the laminate according to [6].
[8] A device film obtained by peeling a carrier substrate from the device laminate according to [7].

By the production method of the present invention, a laminate can be obtained from which a device film having a circuit formed on a polyimide film layer can be easily and efficiently peeled from a carrier substrate.
It is another object of the present invention to provide a laminate having high transparency and durability against ultraviolet rays and capable of easily peeling the carrier substrate and the polyimide film layer contained in the laminate.

Hereinafter, embodiments of the present invention will be described in detail. What is described below is an example (representative example) of an embodiment of the present invention, and the present invention is not limited to the following embodiment unless it exceeds the gist.
<Laminated body manufacturing method>
The method for producing a laminate of the present invention comprises a step of providing a silane coupling layer on a carrier substrate such as glass, a polyamic acid resin solution and / or a polyimide resin solution applied on the silane coupling layer, and drying. A step of providing a polyimide film layer. Other steps and other layers may be provided as necessary.
Examples of other steps include a step of performing cleaning or surface treatment before the step of providing the silane coupling layer on the carrier substrate.

According to the method for manufacturing a laminate of the present invention, there is no need to transfer a separately prepared polyimide film to a carrier substrate, and the polyimide film layer can be formed directly on the carrier substrate having a silane coupling layer. . Moreover, the device in which the circuit etc. were formed on the polyimide film layer is laminated | stacked, and the peeling from the carrier substrate of the polyimide film layer in which the device was laminated | stacked can be made easy. In the method of the present invention, damage to devices such as a polyimide film layer and a circuit during peeling can be reduced, so that the durability of the device can be improved.
In addition, since the present invention provides a polyimide film layer by applying a polyamic acid resin solution and / or a polyimide resin solution and drying it, it is suitable for efficiently producing a thin device and a flexible device that can be bent. It is. In particular, it is a particularly suitable method for efficiently producing display devices such as liquid crystal displays, organic EL displays, and electronic paper, light receiving devices such as solar cells, and light emitting devices such as organic EL lighting.

<Process for forming a device on the laminate>
In the laminate obtained by the present invention, a device is formed on the polyimide film layer on the laminate surface. After forming the device, the polyimide film layer and the device can be peeled off from the carrier substrate and used in various applications such as a display device, a light receiving device, and a light emitting device.
Before laminating the device, the polyimide film layer may be washed or surface-treated as necessary. Moreover, you may laminate | stack various barrier layers on a polyimide film layer as needed. These methods are not limited.
Examples of cleaning include UV ozone cleaning, plasma cleaning, sputter cleaning, ion cleaning, heat cleaning, dry ice jet cleaning, and wet cleaning as water cleaning, alkali cleaning, acid cleaning, and detergent cleaning as examples of dry cleaning. , Solvent cleaning, liquid jet cleaning and the like.
As an example of lamination of various barrier layers, a method of coating a gas barrier polymer, a metal such as platinum or aluminum, an inorganic oxide such as alumina or titanium oxide, a metal nitride, etc. are laminated, and a metal and inorganic thin film coating is applied. And a method of coating an organic barrier layer or an organic / inorganic composite barrier layer.

  Circuits necessary for a display device, a light receiving device, a light emitting device, and the like are formed on the polyimide film layer formed by the above method. This process varies depending on the type of device. For example, when manufacturing a TFT liquid crystal display device, a TFT such as amorphous silicon may be formed on a polyimide film layer. Also, a TFT can be formed by forming a gate metal layer, a silicon nitride gate dielectric layer, and an ITI pixel electrode. Furthermore, a structure necessary for the liquid crystal display can be formed on the TFT by a known method.

The display device is not limited to the TFT liquid crystal display, but includes organic EL displays, liquid crystal displays, electronic paper applications, and the like.
Moreover, a solar cell device etc. are mentioned as a light receiving device, The illumination etc. which used organic EL are mentioned as a light emitting device.
Moreover, when manufacturing a solar cell device, a solar cell using, for example, crystalline silicon, amorphous silicon, a compound semiconductor material, or an organic compound material may be formed on a polyimide film layer. For example, a solar cell can be formed by forming a transparent electrode, crystalline silicon, amorphous silicon, or a photoelectric conversion layer containing an organic material, and a counter electrode. Furthermore, a structure necessary for the solar cell can be formed on the solar cell by a known method.
In addition, you may perform the process which laminates layers other than a circuit, the process of modularizing a member, etc. with respect to the polyimide film layer in which the circuit was formed by the said process.

<Step of peeling the polyimide film layer on which the device is formed from the carrier substrate>
The laminate in which the device is laminated on the polyimide film layer by the above-described method or the like peels off the carrier substrate and the polyimide film layer. In the present invention, it is presumed that the silane coupling layer provided between the carrier substrate and the polyimide film layer is bonded to the carrier substrate and remains largely on the carrier substrate side.
In this invention, the device laminated | stacked on the polyimide film layer and layer after peeling a carrier substrate and a polyimide film layer is represented as a device film.

  There is no restriction | limiting in particular in the peeling method of a carrier substrate and a polyimide film layer, For example, the method of irradiating a laser etc. from the carrier substrate side, the method of immersing in water, the method of physically peeling, etc. are mentioned. However, the physical peeling method is particularly preferable in that it can be peeled without impairing the performance of the device formed on the polyimide film layer.

The method of physically peeling is, for example, a method of obtaining a device film by cutting off the peripheral edge of the device on the polyimide film layer on the carrier substrate, or a method of obtaining a device film by sucking the peripheral edge of the device on the polyimide film layer A method of obtaining a device film by fixing the periphery of the device on the polyimide film layer and moving only the carrier substrate, and the like.
In order to use such a method of physically peeling, in the peeling test according to JIS K 6854-2, the peeling strength between the carrier substrate and the polyimide film layer needs to be larger than 0 N / m. If it is 0 N / m, in the process of forming a device on the laminate, the polyimide film layer may be displaced or peeled off from the carrier substrate.
In an actual manufacturing process, a film formed on a carrier substrate may be cut with a laser or a cutter, and then the film may be peeled off. In that case, it is preferable that the film is not peeled until the cut is made, and the peel strength after the cut is preferably a smaller value.
Therefore, the peel strength between the carrier substrate and the polyimide film layer is greater than 0 N / m, preferably 0.5 N / m or more, more preferably 1 N / m or more, while usually 1.0 × 10 ³ N / m. Hereinafter, it is preferably 7.0 × 10 ² N / m or less. When the peel strength is in the above range, the polyimide film layer tends not to peel or shift from the carrier substrate in the device formation process. Moreover, it exists in the tendency which can peel a device film from a carrier substrate easily, without damaging the device laminated | stacked on the polyimide film layer.

  Examples of the device in the present invention include a display device such as a liquid crystal display, an organic EL display, and electronic paper, a light receiving device such as a solar cell, and a light emitting device such as organic EL illumination. In particular, it is most suitable for application to a device that is desired to be thin, light and flexible.

  Hereinafter, the step of providing a silane coupling layer on the carrier substrate of the present invention, and applying a polyamic acid resin solution and / or a polyimide resin solution on the silane coupling layer provided on the surface of the carrier substrate and drying the polyimide The step of providing the film layer will be described in detail.

<Step of providing a silane coupling layer on a carrier substrate>
In the step of providing the silane coupling layer on the carrier substrate, the method for providing the silane coupling layer is not particularly limited. Specifically, a method of applying and drying a solution containing a silane coupling agent and a solvent on a carrier substrate and then heat-treating, dipping and heating the carrier substrate in a solution containing a silane coupling agent and a solvent Examples thereof include a method, a method in which a polyamic acid resin solution and / or a polyimide resin solution mixed with a silane coupling agent is applied to a carrier substrate and dried.

  The film thickness of the silane coupling layer provided on the carrier substrate is not particularly limited. In order to obtain a sufficient peeling effect, the thickness is preferably 1 nm or more, and more preferably 10 nm or more. In addition, the upper limit is appropriately determined depending on the application, and is not particularly limited. However, it is 0.5 μm or less, in the process of laminating the device on the carrier substrate, elution of substances derived from the silane coupling layer by washing or the like This is preferable because there is a tendency to reduce the degassing component during the high-temperature process.

  The carrier substrate used in the production method of the present invention is preferably hard and heat resistant. That is, it is preferable to use a material that does not deform under the temperature conditions required in the manufacturing process. Specifically, the carrier substrate is preferably made of a material having a glass transition temperature of usually 200 ° C. or higher, preferably 250 ° C. or higher. In order to reduce the manufacturing cost of the device, it is also preferable to use an inexpensive carrier substrate. From such a viewpoint, preferable examples of the material of the carrier substrate include glass, ceramic, metal, silicon wafer and the like.

  Although it does not specifically limit as a glass substrate used as a material of a carrier substrate, For example, a blue plate glass (alkali glass), high silicate glass, soda lime glass, lead glass, aluminoborosilicate glass, non-alkali Examples thereof include glass (borosilicate glass, Corning Eagle XG, etc.) and aluminosilicate glass.

  The manufacturing method of the present invention is inexpensive but damages the polyimide film layer and the device laminated on the polyimide film layer even when glass having very strong adhesion to the polyimide film layer is used as the carrier substrate. And can be peeled off. Therefore, a device can be manufactured at a low cost in a shorter process.

  The thickness of the carrier substrate is not particularly limited, but is usually 0.3 mm or more, preferably 0.5 mm or more, and is usually 5.0 cm or less, preferably 2.0 cm or less. When the thickness of the carrier substrate is within such a range, the impact resistance of the carrier substrate can be improved and the device manufacturing cost can be reduced.

In the step of providing the silane coupling layer on the carrier substrate of the present invention, the silane coupling agent to be used is not particularly limited, but at least one silane coupling agent selected from the general formulas (1) to (3) is used. However, it is preferable for obtaining peelability from the carrier substrate.
One silane coupling agent represented by the general formulas (1) to (3) may be used, or a plurality of silane coupling agents may be used in combination. Moreover, you may use together with coupling agents, such as a titanate coupling agent and an aluminum coupling agent.

The solvent to be combined with the silane coupling agent is not particularly limited, but water, a water-soluble organic solvent and the like are preferable because of the solubility of the silane coupling agent.
One type of water and water-soluble organic solvent may be used, or a plurality may be used in combination. Further, the silane coupling solution used for the silane coupling treatment may contain a pH adjuster, a surfactant, or the like. The mixing method and procedure of these arbitrary components are not particularly limited.

Specific examples of the water-soluble organic solvent include alcohols such as methanol, ethanol, isopropyl alcohol, n-butanol, isobutyl alcohol, and n-propyl alcohol; ethylene glycol, ethylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, and the like. Glycol ethers; ketones such as acetone, methyl ethyl ketone, diethyl ketone, methyl propyl ketone, methyl isobutyl ketone, cyclohexanone; furans such as tetrahydrofuran; N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2 -Amines such as pyrrolidone.
Among these, alcohols and ketones are preferable, and alcohols are more preferable from the viewpoint of solubility of the silane coupling agent.
In addition, when A ^{1 to} A ⁴ in the general formula (1) and Y ^{2 in the} general formula (2) include a hydrophobic group such as an alkyl group, a silane coupling agent is added in advance to methanol or water in order to promote water solubilization. It is preferable to dissolve in alcohols such as ethanol and isopropyl alcohol.

  The drying and heating methods after applying or impregnating the carrier substrate with a solution containing a silane coupling agent and a solvent are not particularly limited. Examples of drying include natural drying and heat drying. Moreover, when desiring to shorten the drying time, it is preferable to heat at 50 ° C to 150 ° C.

  As the silane coupling agent used in the step of providing the silane coupling layer on the carrier substrate, it is preferable to use at least one selected from the following general formulas (1) to (3).

(In general formula (1),
A ^{1 to} A ⁴ each independently represents an organic group that does not contain an epoxy group and an amino group,
At least one of A ^{1 to} A ⁴ represents an alkoxy group which may have a substituent, an acyloxy group which may have a substituent, or a halogen atom. )

(In General Formula (2), A ^{5 to} A ⁷ each independently have an alkyl group which may have a substituent, an acyl group which may have a substituent, or a substituent. The alkyl group, the acyl group, and the substituent that the aromatic group may have does not include an epoxy group and an amino group, and Y ¹ does not include an epoxy group and an amino group, An organic group, m ¹ represents an integer of 2 or more, and a plurality of Y ¹ and A ⁷ present in one molecule of the silane coupling agent represented by the general formula (2) may be the same or different. .)

(In General Formula (3), A ^{8 to} A ¹³ each independently have an alkyl group which may have a substituent, an alkoxy group which may have a substituent, or a substituent. An acyloxy group which may be present, and the substituent which the alkyl group, alkoxy group and acyloxy group may have does not include an epoxy group and an amino group,
X ¹ represents a —NH— group or a group represented by the following general formula (4).

(In General Formula (4), R ¹ and R ² each independently represents an alkyl group which may have a substituent, and the substituent which the alkyl group may have includes an epoxy group and an amino group. No group is included, and m ² represents an integer of 1 or more.)

<About General Formula (1)>
A ^{1 to} A ^{4 in} the general formula (1) each independently represents an organic group that does not contain an epoxy group and an amino group. Since it has an epoxy group and an amino group, it reacts with the functional group of the polyamic acid resin and / or polyimide resin formed on the silane coupling layer, so that the silane coupling layer and the polyimide film layer adhere firmly, and the carrier Peeling from the substrate becomes difficult.
In the present invention, A ¹ to A ⁴ in the general formula (1) is an organic group containing no epoxy group and an amino group. By providing the silane coupling layer on the carrier substrate using the silane coupling agent represented by the general formula (1), the intermolecular interaction between the carrier substrate and the polyimide film layer is lowered. Therefore, the adhesiveness between the carrier substrate and the polyimide film layer is lowered and peeling becomes easy.
In patent document 2 mentioned above, in order to make peeling of a polyimide film layer easy, the silane coupling agent which has an epoxy group and an amino group is used. However, these silane coupling agents are effective when laminating separately produced polyimide films by heating and pressurization, and in the production method of the present invention, the peel strength is increased, and thus the reverse effect and Become.

In addition, at least one of A ^{1 to} A ⁴ represents an alkoxy group which may have a substituent, an acyloxy group which may have a substituent, or a halogen atom substituent.
Among A ^{1 to} A ⁴ , the ratio of an alkoxy group which may have a substituent, an acyloxy group which may have a substituent, or a halogen atom is 1 or more, but not particularly limited. The following is preferable. By being in this range, it is possible to prevent a decrease in applicability of the polyamic acid resin solution and / or the polyimide resin solution and formation of defects in the polyimide film layer due to aggregation of the silane coupling agent.

The alkoxy group which may have a substituent of A ^{1 to} A ⁴ is represented by —OR ¹¹ group, and R ¹¹ is a hydrogen atom, an alkyl group which may have a substituent or a substituent. The aromatic group which may have is shown.
The alkyl group for R ¹¹ is not particularly limited, and specifically includes methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, Linear alkyl group such as dodecyl group; branched alkyl group such as isopropyl group, isobutyl group, sec-butyl group, tert-butyl group, isooctyl group, isononyl group; cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, And cyclic alkyl groups such as a cyclopropylmethyl group, a cyclohexylmethyl group, and a 4-butylmethylcyclohexyl group. Among these, the number of carbon atoms is preferably 1 or more, preferably 20 or less, more preferably 15 or less. By being the said range, there exists a tendency for the time which forms the silane coupling layer to a carrier substrate to become short.

The substituent which the alkyl group of R ¹¹ may have is not particularly limited, but specifically, from the viewpoint of improving the peelability between the carrier substrate and the polyimide film layer, an alicyclic hydrocarbon group, aromatic Aromatic group such as aromatic hydrocarbon group and aromatic heterocyclic group, alkenyl group, halogen atom, shear / BR> M group, isocyanate group, alkylthio group, sulfanyl group, acrylic group, methacryl group, sulfide group, acyl group or An alkoxy group etc. are mentioned.

The aromatic group for R ¹¹ is not particularly limited, and examples thereof include an aromatic hydrocarbon group which may have a substituent and an aromatic heterocyclic group which may have a substituent.
Examples of the aromatic hydrocarbon group which may have a substituent include a phenylene group, a biphenylene group, a naphthylene group, a phenanthrene group, a triphenylene group, a terphenylene group, a pinylene group, and a fluorene group. Among these, 5 or more carbon atoms are preferable, and 30 or less, and further 25 or less are preferable.
Among the aromatic groups that may have a substituent of R ¹¹ , a benzene ring, a biphenylene ring, and a terphenyl ring are preferable because the time for forming a silane coupling layer on a carrier substrate tends to be shortened.

Examples of the aromatic heterocyclic group which may have a substituent of R ¹¹ include a pyridylene group, a quinolylene group, a thiophene ring, a furan ring, a pyrrole ring, a pyrazole ring, a thiazole ring and an oxazole ring. Among these, 2 or more carbon atoms are preferable, 30 or less, and further 25 or less are preferable. When the carbon number of the aromatic group and aromatic heterocyclic group of R ¹¹ is in the above range, the time for forming the silane coupling layer on the carrier substrate tends to be shortened.
Examples of the substituent that the aromatic group of R ¹¹ may have include a halogen atom, an alkyl group, an alkoxy group, and a hydroxyl group.
Examples of the halogen atom include a fluorine atom, a bromine atom, and a chlorine atom. Examples of the alkyl group include those having 1 to 20 carbon atoms such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, and a tertiary butyl group. Examples of the alkoxy group include those having 1 to 20 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, and a tertiary butoxy group.

As described above, A ^{1 to} A ^{4 in} the general formula (1) are an organic group that does not contain an epoxy group and an amino group, and at least one of them may have a substituent. There is no particular limitation as long as it is an acyloxy group which may have a halogen atom or a halogen atom.
In A ^{1 to} A ⁴ , specific examples other than an optionally substituted alkoxy group, an optionally substituted acyloxy group, or a halogen atom may have a substituent. Aromatic group, optionally substituted alkyl group, optionally substituted alkenyl group, optionally substituted alkylthio group, cyano group, isocyanate group, sulfanyl group or substituted And an acyl group which may have a group.
Among these, an aromatic group which may have a substituent or an alkyl group which may have a substituent is particularly preferable because the peelability between the carrier substrate and the polyimide film layer tends to be good.

Specific examples of the aromatic group which may have a substituent of A ^{1 to} A ^{4 and} the alkyl group which may have a substituent may have the substituent of R ¹¹ described above. It is synonymous with the aromatic group and the alkyl group which may have a substituent, respectively, and its preferable range is also synonymous.

In the alkenyl group which may have a substituent of A ^{1 to} A ⁴ , the position of the carbon-carbon unsaturated bond is not particularly limited, and may have a plurality of unsaturated bonds. Moreover, it may be linear or branched and may have an arbitrary substituent.
Examples of the alkenyl group include a vinyl group, an allyl group, a propenyl group, an isopropenyl group, and a hexenyl group. Among them, the carbon number is preferably 1 or more, and the carbon number is 20 or less. Preferably, it is 18 or less. By being the said range, the easy peeling of a polyimide film is enabled, without reducing the coating property of a polyamic acid resin solution and / or a polyimide resin solution.

Examples of the substituent that the alkenyl group of A ^{1 to} A ⁴ may have include an alicyclic hydrocarbon group, an aromatic hydrocarbon group, and an aromatic complex from the viewpoint of improving the peelability between the carrier substrate and the polyimide film layer. An aromatic group such as a ring group, an alkyl group, a halogen atom, a cyano group, an isocyanate group, a sulfanyl group, an acryl group, a methacryl group, a sulfide group, an acyl group, or an alkoxy group.

Specific examples of the acyl group which may have a substituent of A ^{1 to} A ⁴ include a formyl group, an acetyl group, a propionyl group, a butyryl group, an isobutyryl group, a lauroyl group, an acryloyl group, a methacryloyl group, and a propioyl group. And benzoyl group. Among these, the number of carbon atoms is preferably 1 or more, preferably 20 or less, and more preferably 18 or less. By being the said range, the easy peeling of a polyimide film is enabled, without reducing the coating property of a polyamic acid resin solution and / or a polyimide resin solution.
Specifically, the substituents that the acyl groups of A ^{1 to} A ⁴ may have are alicyclic hydrocarbon groups and aromatic hydrocarbons from the viewpoint of improving the peelability between the carrier substrate and the polyimide film layer. Group and aromatic group such as aromatic heterocyclic group, alkenyl group, halogen atom, cyano group, isocyanate group, sulfanyl group, acrylic group, methacryl group, sulfide group, acyl group or alkoxy which may have a substituent Groups and the like.

Specific examples of the alkylthio group which may have a substituent of A ^{1 to} A ⁴ include a methylsulfanyl group and an ethylsulfanyl group. Among these, it is preferable that it is 20 or less carbon atoms, and also it is preferable that it is 18 or less carbon atoms. By being the said range, the easy peeling of a polyimide film is enabled, without reducing the coating property of a polyamic acid resin solution and / or a polyimide resin solution.
Specific examples of the substituent that the alkylthio group of A ^{1 to} A ⁴ may have include an alicyclic hydrocarbon group and an aromatic hydrocarbon from the viewpoint of improving the peelability between the carrier substrate and the polyimide film layer. An aromatic group such as a group and an aromatic heterocyclic group, an alkenyl group, a halogen atom, a cyano group, an isocyanate group, an acrylic group, a methacryl group, a sulfide group, an optionally substituted acyl group or an alkoxy group Can be mentioned.

<About General Formula (2)>
Y ^{2 in the} general formula (2) represents an organic group that does not contain an epoxy group and an amino group. As described above in the general formula (1), when having an epoxy group and an amino group, it reacts with a functional group of a polyamic acid resin and / or a polyimide resin formed on the silane coupling layer. And the polyimide film layer firmly adhere to each other, making it difficult to peel off the carrier substrate. Accordingly, Y ² in the general formula (2) is an organic group not containing an epoxy group and an amino group.
By using the silane coupling agent represented by the general formula (2) and providing the silane coupling layer on the surface of the carrier substrate, the intermolecular interaction between the carrier substrate and the polyimide film layer is lowered. Therefore, the adhesiveness between the carrier substrate and the polyimide film layer is lowered and peeling becomes easy.

Y ² is not particularly limited as long as it is an organic group that does not contain an epoxy group or an amino group, and specifically, an aromatic group that may have a substituent, or an alkyl that may have a substituent. Group, an alkenyl group which may have a substituent, a cyano group, an isocyanate group, an alkylthio group which may have a substituent, a sulfanyl group, or an acyl group which may have a substituent. Can be mentioned.
Among these, an aromatic group which may have a substituent or an alkyl group which may have a substituent is particularly preferable because the peelability between the carrier substrate and the polyimide film layer tends to be good.

Y ² may have an aromatic group which may have a substituent, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, or a substituent. Specific examples, preferred ranges, and optional substituents of the acylthio group and the optionally substituted alkylthio group are the same as R ¹¹ and A ^{1 to} A ^{4 in the} general formula (1), respectively. .

A ⁵ , A ⁶ and A ⁷ in the general formula (2) each independently have an alkyl group which may have a substituent, an acyl group which may have a substituent, and a substituent. An aromatic group that may be present. A ⁵ , A ⁶ and A ⁷ may be the same or different.

The alkyl group which may have a substituent of A ⁵ , A ⁶ and A ⁷ is synonymous with the alkyl group mentioned in the general formula (1) R ¹¹ , and the optionally substituted substituent is also synonymous. is there.
The alkyl group of A ⁵ , A ⁶ and A ⁷ preferably has 1 or more carbon atoms, preferably 10 or less carbon atoms, more preferably 5 or less carbon atoms, particularly 3 or less carbon atoms. preferable. When the carbon number is in an appropriate range, the hydrolysis rate of the silane coupling agent is high, and the time for forming the silane coupling layer on the carrier substrate tends to be shortened.

The acyl group and aromatic group which may have a substituent of A ⁵ , A ⁶ and A ⁷ are respectively synonymous with the acyl group and aromatic group mentioned in general formula (1) R ¹¹ , and are preferable. The number of carbon atoms and the substituent which may be present are also synonymous. When the carbon number is in an appropriate range, the hydrolysis rate of the silane coupling agent is high, and the time for forming the silane coupling layer on the carrier substrate tends to be shortened.

m ¹ is an integer of 2 or more, and there is no particular upper limit as long as the effect of the present invention is not impaired.
It is preferable to appropriately adjust m ¹ depending on the concentration of the desired silane coupling agent.

<About general formula (3)>
A < ⁸ > -A < ¹³ > of General formula (3) shows the alkyl group which may have a substituent, or the alkoxy group which may have a substituent each independently. In addition, each of these groups does not contain an epoxy group or an amino group. As described in the general formulas (1) and (2), when having an epoxy group and an amino group, it reacts with the functional group of the polyamic acid resin and / or polyimide resin formed on the silane coupling layer, The silane coupling layer and the polyimide film layer are firmly bonded, and peeling from the carrier substrate becomes difficult. Therefore, A < ⁸ > -A < ¹³ > of General formula (3) is an organic group which does not contain an epoxy group and an amino group.

The alkyl group which may have a substituent of A ^{8 to} A ¹³ is specifically synonymous with the alkyl group represented by R ¹¹ in the general formula (1), and the substituent which may have It is synonymous. The alkyl groups of A ^{8 to} A ¹³ each independently preferably have 1 or more carbon atoms, preferably 10 or less carbon atoms, and more preferably 5 or less carbon atoms. By being the said range, the easy peeling of a polyimide film is enabled, without reducing the coating property of a polyamic acid resin solution and / or a polyimide resin solution.

The alkoxy group which may have a substituent of A ^{8 to} A ¹³ is represented as an —OR ¹² group. R ¹² represents a hydrogen atom, an alkyl group which may have a substituent, or an aromatic group which may have a substituent, and specifically has the same meaning as R ^{11 in} formula (1). The preferable group and the substituent which may have are also synonymous.

X ¹ represents a —NH— group or a group represented by the general formula (4).

In General Formula (4), R ¹ and R ² each independently represents an alkyl group which may have a substituent, and does not have an epoxy group or an amino group. m ² is an integer of 1 or more.

By treating the carrier substrate with the silane coupling agent represented by the general formula (3), the intermolecular interaction between the carrier substrate and the polyimide is reduced. Therefore, the adhesiveness between the carrier substrate and the polyimide film layer is lowered and peeling becomes easy.
Incidentally, when ^{X 1} is a -NH- group, -NH- moiety, to form ammonia by hydrolysis, it does not react with the polyimide film layer.

The alkyl group which may have a substituent of R ¹ and R ² is specifically synonymous with the alkyl group represented by R ¹¹ in the general formula (1), and the substituent which may have It is synonymous. The alkyl group for R ¹ and R ² preferably has 1 or more carbon atoms, preferably 10 or less carbon atoms, and more preferably 5 or less carbon atoms. When the carbon number is in an appropriate range, the polyimide film can be easily peeled without lowering the coating property of the polyamic acid resin solution and / or the polyimide resin solution.
m ² represents an integer of 1 or more, and the upper limit is not particularly limited as long as the effect of the present invention is not impaired, and can be adjusted as appropriate.

Although the specific example of the silane coupling agent represented by General formula (1) of this invention is shown below, it is not limited to this.
Examples of the silane coupling agent in which at least one of A ^{1 to} A ⁴ is an alkyl group include methyltrimethoxysilane, dimethyldimethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, triethoxyethylsilane, propyltrimethoxysilane, and propyl. Triethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, pentyltriethoxysilane, octyltriethoxysilane, decyltrimethoxysilane, dodecyltriethoxysilane, hexadecyltrimethoxysilane, octadecyltriethoxysilane, octadecyltrimethoxysilane, Trimethylmethoxysilane, ethyltrimethoxysilane, diisopropyldimethoxysilane, isobutyltrimethoxysilane, diisobutyldimethoxysilane Isobutyltriethoxysilane, cyclohexyltrimethoxysilane, cyclohexylmethyldimethoxysilane, butyltrichlorosilane, cyclohexyltrichlorosilane, decyltrichlorosilane, dodecyltrichlorosilane, ethyltrichlorosilane, trichlorohexylsilane, methyltrichlorosilane, trichlorooctadecylsilane, octyltrichlorosilane , Trichlorotetradecylsilane, methyltriphenoxysilane, triacetoxymethylsilane, diacetoxydimethylsilane, and the like.

Examples of the silane coupling agent in which at least one of A ^{1 to} A ⁴ is an alkyl group having a substituent include 3-chloropropyltrimethoxysilane, 3-chloropropyldimethoxymethylsilane, and (chloromethyl) triethoxysilane. , 3-chloropropyltriethoxysilane, triethoxy-1H, 1H, 2H, 2H-tridecafluoro-n-octylsilane, trimethoxy (3,3,3-trifluoropropyl) silane, triethoxy (1H, 1H, 2H, 2H-nonafluorohexyl) silane, 3-chloropropyltrichlorosilane, trichloro (1H, 1H, 2H, 2H-tridecafluoro-n-octyl) silane, trichloro (1H, 1H, 2H, 2H-heptadecafluorodecyl) And silane.

Examples of the silane coupling agent in which at least one of A ^{1 to} A ⁴ is an aromatic group include phenyltriethoxysilane, phenyltrimethoxysilane, dimethoxydiphenylsilane, dimethoxymethylphenylsilane, phenyltrichlorosilane, and trichloro (phenylethyl) silane. , Trichloro (3-phenylpropyl) silane, trichloro (6-phenylhexyl) silane, and the like.

Examples of the silane coupling agent in which at least one of A ^{1 to} A ⁴ is an alkenyl group (vinyl group) include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane, diethoxymethylvinylsilane, dimethoxymethylvinylsilane, tris ( 2-methoxyethoxy) vinylsilane, trichlorovinylsilane, allyltrimethoxysilane, allyltriethoxysilane, allyltrichlorosilane, p-styryltrimethoxysilane and the like.

Examples of the silane coupling agent in which at least one of A ^{1 to} A ⁴ is an acyl group (acryloyl group, methacryloyl group) include 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, and 3-methacryloxypropyl. Examples thereof include methyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, and 3-acryloxypropyltrimethoxysilane.

Examples of the silane coupling agent in which at least one of A ^{1 to} A ⁴ is an alkylthio group and a sulfanyl group include 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, and 3-octanoylthio. Examples include -1-propyltriethoxysilane.

Examples of the silane coupling agent in which at least one of A ^{1 to} A ⁴ is an isocyanate group include 3-isocyanatopropyltriethoxysilane and 3-isocyanatepropyltrimethoxysilane.

Examples of the silane coupling agent in which at least one of A ^{1 to} A ⁴ is a cyano group include 2-cyanoethyltriethoxysilane and 2-cyanoethyltrichlorosilane.

Examples of the silane coupling agent having an alkoxy group in all of A ^{1 to} A ⁴ include tetraethoxysilane.

Although the specific example of the silane coupling agent represented by General formula (2) of this invention is shown below, it is not limited to this.
Polydimethylsiloxane, methylmethoxysiloxane, dimethylphenylmethoxysiloxane, alkylalkoxysiloxane, alkoxy oligomer (product names KC-89S, KR-500, X40-9225, X-40-9246, X-40-9250, KR-401N, X-40-9227, X-40-9247, KR-510, KR-9218, KR-213 (manufactured by Shin-Etsu Chemical Co., Ltd.)) and the like.

  Specific examples of the silane coupling agent represented by the general formula (3) of the present invention include bis (triethoxysilylpropyl) tetrasulfide and hexamethyldisilazane.

  Among the silane coupling agents of the present invention, in particular, the use of the silane coupling agent represented by the general formula (1) and / or the general formula (2) has good releasability between the carrier substrate and the polyimide film layer. preferable.

<Process of providing a polyimide film layer>
The method for producing a laminate of the present invention includes a polyamic acid resin solution and / or a polyimide resin solution on a silane coupling layer provided on a carrier substrate surface obtained by the step of providing a silane coupling layer on the carrier substrate described above. It has the process of providing a polyimide film layer by apply | coating and drying (henceforth a process of providing a polyimide film layer).
In the present invention, a polyimide film layer is formed by applying a polyamic acid resin solution and / or a polyimide resin solution onto a carrier substrate having a silane coupling layer, and evaporating and drying the solvent, followed by heating. Can do.

  When forming the polyamic acid resin solution and / or the polyimide resin solution on the silane coupling layer provided on the carrier substrate, either the polyamic acid resin solution and / or the polyimide resin solution may be used. Moreover, you may mix and use two types.

  The solvent for dissolving the polyamic acid resin or polyimide resin of the present invention is not particularly limited. Examples of the solvent include amide solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, and N-methyl-2-pyrrolidone; aprotic solvents such as dimethyl sulfoxide and γ-butyrolactone; It is done. Among these, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, and γ-butyrolactone are particularly preferable. These solvents may be one kind or a mixture of two or more kinds.

The concentration of the polyamic acid resin solution and / or the polyimide resin solution is not particularly limited, but is usually 1% by mass or more, preferably 5% by mass or more, and usually 80% by mass or less, preferably 50% by mass. It is as follows. By adjusting the concentration of the polyimide resin in the composition within this range, good coatability can be achieved.
The solution viscosity of the polyamic acid resin solution and / or polyimide resin solution of the present invention is not particularly limited, but is usually 10 mPa · s or more, preferably 1.0 × 10 ² mPa · s or more, while usually It is 5.0 × 10 ⁴ mPa · s or less, preferably 2.0 × 10 ⁴ mPa · s or less. By adjusting the viscosity of the polyamic acid resin solution and / or the polyimide resin solution within the above range, good coatability can be achieved. The solution viscosity is measured at 25 ° C. using an E-type viscometer. The solution viscosity can be measured by a known method, for example, according to the method described in International Publication No. 99/60622.

When a mixed solution obtained by adding a polyamic acid resin solution to a polyimide resin solution is applied to a carrier substrate and dried to form a polyimide film, the adhesion between the polyimide film and the carrier substrate can be controlled. For example, increasing the proportion of the polyamic acid resin solution tends to improve the adhesion between the formed polyimide film and the carrier substrate.
Thus, the adhesive strength of the polyimide film can be controlled in consideration of the material of the carrier substrate also by adjusting the material composition ratio in the polyimide resin solution.

  The ratio of the polyamic acid resin solution to the polyimide resin solution in the polyimide resin solution is not particularly limited, but is usually 30% or less, preferably 20% or less, and more preferably 10% or less. If the polyimide resin solution contains 30% or more of the polyamic acid resin solution, the polyimide resin and the polyamic acid resin may be phase-separated to cause white turbidity.

  The method of applying the polyamic acid resin solution and / or the polyimide resin solution to the carrier substrate having a silane coupling layer is not particularly limited as long as it can form a layer having a uniform thickness on the carrier substrate. Examples include die coating, spin coating, screen printing, spraying, a casting method using an applicator, a method using a coater, a spraying method, a dipping method, a calendar method, and a casting method.

  The thickness of the obtained polyimide film layer can be controlled by adjusting the amount of the polyamic acid resin solution and / or the polyimide resin solution applied. The thickness of the polyimide film layer is usually 1 μm or more, preferably 2 μm or more, and is usually 300 μm or less, preferably 200 μm or less. When the thickness is 1 μm or more, the polyimide film layer can have sufficient strength. This is preferable in that the strength of the device provided on the polyimide film layer is improved and the device is not easily damaged. Moreover, since it becomes possible to make the device containing the polyimide film layer obtained thin by making thickness into 200 micrometers or less, it is preferable. In order to obtain a thinner device having sufficient strength, the thickness of the polyimide film layer is more preferably 2 to 200 μm.

  A method for volatilizing the solvent of the polyamic acid resin solution and / or the polyimide resin solution is not particularly limited. Usually, the solvent is volatilized by heating the carrier substrate coated with the polyamic acid resin solution and / or the polyimide resin solution. The heating method is not particularly limited, and examples thereof include hot air heating, vacuum heating, infrared heating, microwave heating, heating by contact using a hot plate or a hot roll.

  The heating temperature in this case may be a suitable temperature depending on the type of solvent, but is usually 40 ° C. or higher, preferably 60 ° C. or higher, and is usually 400 ° C. or lower, preferably 350 ° C. or lower, more preferably. Is 300 ° C. or lower. When the solvent removal temperature is 40 ° C. or higher, it is preferable in that the solvent is sufficiently volatilized. Further, when the solvent removal temperature is 300 ° C. or lower, since the organic solvent does not volatilize rapidly, it is possible to prevent bubbles from being generated in the obtained polyimide film layer. This is preferable because the possibility of reducing the appearance and quality of the resulting polyimide film layer can be reduced. The heating atmosphere may be air or an inert atmosphere, and is not particularly limited. However, when the polyimide film layer is required to be colorless and transparent, it is heated under an inert atmosphere such as nitrogen to suppress coloring. It is preferable to do.

<Method for producing polyamic acid resin solution and polyimide resin solution>
The manufacturing method of the polyamic acid resin solution and the polyimide resin solution of the present invention is not particularly limited. Hereinafter, raw materials for the polyamic acid resin solution and the polyimide resin solution are shown.
Furthermore, the manufacturing method of a polyamic acid resin solution and the method of obtaining a polyimide resin solution are demonstrated.

<Raw materials for polyamic acid resin solution and polyimide resin solution>
Examples of the raw material for the polyamic acid resin solution include tetracarboxylic dianhydrides and diamine compounds. Moreover, tetracarboxylic dianhydride, a diamine compound, and a diisocyanate compound are mentioned as a raw material of a polyimide resin solution.
Examples of tetracarboxylic dianhydrides include aromatic tetracarboxylic dianhydrides, aromatic tetracarboxylic dianhydrides containing fluorine groups, and aliphatic tetracarboxylic dianhydrides. Examples of the diisocyanate include aromatic diisocyanate compounds and aliphatic diisocyanate compounds. Examples of the diamine compound include aromatic diamine compounds, aromatic diamine compounds containing a fluorine group, and aliphatic diamine compounds. Specific examples are shown below.

(Aromatic tetracarboxylic dianhydrides)
Examples of the aromatic tetracarboxylic dianhydrides include one aromatic ring contained in the molecule such as pyromellitic dianhydride and 1,2,3,4-benzenetetracarboxylic dianhydride. Tetracarboxylic dianhydride;
1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride, bis (2,3-dicarboxyphenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, 3 , 3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 1,1′-biphenyl-3,3 ′, 4,4′-tetracarboxylic dianhydride, 2,2-bis (3,4) -Dicarboxyphenyl) propane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propane dianhydride, 3,3 ', 4,4'-diphenylsulfonetetracarboxylic dianhydride, bis ( 3,4-dicarboxyphenyl) ether dianhydride, bis (2,3-dicarboxyphenyl) ether dianhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, 2,2 ′ , 3,3'-Benzophenone Lacarboxylic dianhydride, 4,4-oxydiphthalic dianhydride, 4,4- (p-phenylenedioxy) diphthalic dianhydride, 4,4- (m-phenylenedioxy) diphthalic dianhydride, Tetracarboxylic dianhydrides having two or more independent aromatic rings, such as 2,2 ′, 6,6′-biphenyltetracarboxylic dianhydride;
1,2,5,6-naphthalenedicarboxylic dianhydride, 1,4,5,8-naphthalenedicarboxylic dianhydride, 2,3,6,7-naphthalenedicarboxylic dianhydride, 3,4,9 , 10-perylenetetracarboxylic dianhydride, 2,3,6,7-anthracenetetracarboxylic dianhydride, and 1,2,7,8-phenanthrenetetracarboxylic dianhydride Tetracarboxylic dianhydride; and the like.

(Aromatic tetracarboxylic dianhydrides containing fluorine groups)
Examples of the aromatic tetracarboxylic dianhydride containing a fluorine group include 2,2-bis (3,4-dicarboxyphenyl) -1,1,1,3,3,3-hexafluoropropane dianhydride. 2,2-bis (2,3-dicarboxyphenyl) -1,1,1,3,3,3-hexafluoropropane dianhydride, 1,4-difluoropyromellitic dianhydride, 1, 4-ditrifluoromethylpyromellitic dianhydride, etc. are mentioned.

(Aliphatic tetracarboxylic dianhydride)
Examples of the aliphatic tetracarboxylic dianhydride include chains such as ethylene tetracarboxylic dianhydride, butane tetracarboxylic dianhydride, meso-butane-1,2,3,4-tetracarboxylic dianhydride, and the like. Aliphatic aliphatic tetracarboxylic dianhydrides;
1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 1 , 2,3,4-Cyclohexanetetracarboxylic dianhydride, 4- (2,5-dioxotetrahydrofuran-3-yl) -1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic anhydride 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, 1,2,3,4-tetramethyl-1,2,3,4- Cyclobutanetetracarboxylic dianhydride, tricyclo [6.4.0.0 ^2,7 ] dodecane-1,8: 2,7-tetracarboxylic dianhydride, bicyclo [2.2.2] oct-7- En-2, 3, 5 , 6-tetracarboxylic dianhydride, bicyclo [2.2.1] heptane-2,3,5,6-tetracarboxylic dianhydride, 3,3 ′, 4,4′-biscyclohexanetetracarboxylic acid And alicyclic tetracarboxylic dianhydrides such as 1,1′-bicyclohexane-3,3 ′, 4,4′-tetracarboxylic dianhydride; and the like.

(Aromatic diisocyanate compound)
Examples of the aromatic diisocyanate compound include 4,4′-diisocyanato-3,3′-dimethylbiphenyl, 2,2-bis (4-isocyanatophenyl) hexafluoropropane, 4,4′-diisocyanato-3,3. '-Dimethyldiphenylmethane, 1,5-diisocyanatonaphthalene, methylenediphenyl 4,4'-diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 1,3-bis (isocyanatomethyl) ) Benzene, toluene diisocyanate and the like.

(Aliphatic diisocyanate compound)
Examples of the aliphatic diisocyanate compound include 1,3-bis (isocyanatomethyl) cyclohexane, hexamethylene diisocyanate, and isophorone diisocyanate.

(Aromatic diamine compound)
Examples of the aromatic diamine compound include 1,4-phenylenediamine, 1,2-phenylenediamine, 1,3-phenylenediamine, 3-aminobenzylamine, 2,5-dimethyl-1,4-phenylenediamine, p A diamine compound having one aromatic ring in the molecule, such as xylylenediamine, m-xylylenediamine, 2,3,5,6-tetramethyl-1,4-phenylenediamine;
4,4′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, 1,3-bis (4-aminophenoxy) neopentane, 4,4′-diamino-3,3′-dimethylbiphenyl, 4,4′-diamino -2,2'-dimethylbiphenyl, 4,4'-diamino-3,3'-dihydroxybiphenyl, bis (4-amino-3-carboxyphenyl) methane, 4,4'-diaminodiphenyl sulfone, 4,4 ' -Diaminodiphenyl sulfide, N- (4-aminophenoxy) -4-aminobenzamide, 2,7-diaminofluorene, 1,1-bis (4-aminophenyl) cyclohexane, bis (3-aminophenyl) sulfone, 3, 3'-diaminobenzophenone, 4,4'-diaminobenzophenone, 4,4'-diamino-3,3'-dimethyldipheni Methane, 3,3′-diaminodiphenylmethane, 3,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylmethane, 4,4′-ethylenedianiline, 4,4′-methylenebis (2,6-diethylaniline), 4,4′-methylenebis (2-ethyl-6-methylaniline), 4,4′-diamino-2,2′-dimethoxybiphenyl, 2,3′-diaminodiphenyl ether, bis (4-aminophenoxy) methane, , 3′-bis (4-aminophenoxy) propane, 1,4′-bis (4-aminophenoxy) butane, 1,5′-bis (4-aminophenoxy) pentane, 2,2-bis (3-amino) -4-hydroxyphenyl) propane, bis (3-amino-4-hydroxyphenyl) sulfone, N, N-bis (4-aminophenyl) piperazine, etc. A diamine compound having two aromatic rings;
1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) -2,5-di-t-butylbenzene, 1 , 4-bis (4-aminophenoxy) -2,3,5-trimethylbenzene, N, N-bis (4-aminophenyl) terephthalamide, 1,3-bis (3-aminophenoxy) benzene, α, α Diamine compounds having three independent aromatic rings such as' -bis (4-aminophenyl) -1,4-diisopropylbenzene and 1,3-bis [1- (4-aminophenyl) -1-methylethyl] benzene ;
2,2-bis (4- (4-aminophenoxy) phenyl) propane, bis (4- (4-aminophenoxy) phenyl) sulfone, bis (4- (3-aminophenoxy) phenyl) sulfone, 4,4 ′ -Bis (4-aminophenoxy) biphenyl, 4,4 '-(9-fluorenylidene) dianiline, 4,4'-(biphenyl-2,5-diylbisoxy) bisaniline, 4,4'-bis (4-aminobenzamide) ) Diamine compounds having four independent aromatic rings such as -3,3'-dihydroxybiphenyl, 4,4'-bis (4-aminophenoxy) benzophenone, and the like;
2- (4-aminophenyl) -6-aminobenzoxazole, 2- (4-aminophenyl) -5-aminobenzoxazole, 5-amino-2- (4-aminophenyl) -1H-benzimidazole, 1, And a diamine compound having a condensed aromatic ring such as 5-diaminonaphthalene and 3,7-diamino-2,8-dimethyldibenzothiophene 5,5-dioxide.

(Aromatic diamine compounds containing fluorine groups)
As an aromatic diamine compound containing a fluorine group, for example, 5-trifluoromethyl-1,3-benzenediamine, 4,4′-diamino-2,2′-bis (trifluoromethyl) biphenyl, 4,4 '-Diamino-2,2'-bis (trifluoromethyl) biphenyl ether, 2,2'-bis (4-aminophenyl) hexafluoropropane, 2,2'-bis (3-aminophenyl) hexafluoropropane, 4,4′-diaminooctafluorobiphenyl, 2,2-bis (3-amino-4-methylphenyl) hexafluoropropane, 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, 4, 4′-diamino-2- (trifluoromethyl) diphenyl ether, 1,4-bis {4-amino-2- (trifluoromethyl) phenoxy Si} benzene, 2,2-bis (4- (4-aminophenoxy) phenyl) hexafluoropropane, 2,2-bis [4- {4-amino-2- (trifluoromethyl) phenoxy} phenyl] hexafluoro Examples include propane.

(Aliphatic diamine compound)
Examples of the aliphatic diamine compound include 1,3-bis (aminomethyl) cyclohexane, 1,4-bis (aminomethyl) cyclohexane, 1,4-diaminocyclohexane, 4,4′-methylenebis (cyclohexylamine), 4 , 4′-methylenebis (2-methylcyclohexylamine) and the like.

In the above raw materials, when colorless transparency is required as the performance of the polyimide film layer, the following combinations are preferred examples.
A. B. Combinations of aromatic tetracarboxylic dianhydrides and aliphatic diamines or aliphatic diisocyanates Aliphatic tetracarboxylic dianhydrides and aromatic diamines and / or aliphatic diamines C.I. C. Combinations of aliphatic tetracarboxylic dianhydrides with aromatic diisocyanates and / or aliphatic isocyanates Combination of fluorine-containing aromatic tetracarboxylic dianhydrides with fluorine-containing aromatic diamines or fluorine-containing aromatic isocyanates

  In the above raw material, when the heat resistance and dimensional stability of the resulting polyimide film layer are required, it is preferable to use aromatic tetracarboxylic dianhydrides and aromatic diamines. By using these as raw materials, the polyimide film layer tends to have a glass transition point of 300 ° C. or higher, and tends to have a linear expansion coefficient of 10 ppm or lower.

<Method for producing polyamic acid resin solution>
The polyamic acid resin in the polyamic acid resin solution used in the present invention is obtained by reacting at least one of the tetracarboxylic dianhydrides and at least one of the diamine compounds in a suitable solvent.
The polyamic acid ester resin is diesterified by ring-opening the tetracarboxylic dianhydride with an alcohol such as methanol, ethanol, isopropanol, or n-propanol, and the obtained diester is converted into the above-mentioned diester in an appropriate solvent. It can be obtained by reacting with a diamine compound. Furthermore, the polyamic acid ester resin can also be obtained by esterifying the carboxylic acid group of the polyamic acid resin obtained as described above by reacting with the alcohol as described above.

Reaction of the said tetracarboxylic dianhydride and the said diamine compound can be performed on conventionally known conditions. There are no particular limitations on the order of addition or addition method of the tetracarboxylic dianhydride and the diamine compound.
For example, a tetraamic acid dianhydride and a diamine compound are put into a solvent in order, and a polyamic acid resin can be obtained by stirring at an appropriate temperature.
The amount of the diamine compound is usually 0.8 mol or more, preferably 1 mol or more with respect to 1 mol of tetracarboxylic dianhydride. On the other hand, it is 1.2 mol or less normally, Preferably it is 1.1 mol or less. By making the quantity of a diamine compound into such a range, it exists in the tendency for the yield of the polyamic acid resin obtained to improve.

  The concentration of the tetracarboxylic dianhydride and the diamine compound in the solvent can be appropriately set according to the reaction conditions and the viscosity of the polyamic acid resin solution. For example, the total weight of the tetracarboxylic dianhydride and the diamine compound is not particularly limited, but is usually 1% by mass or more, preferably 5% by mass or more with respect to the total amount of the solution, while usually 70%. It is not more than mass%, preferably not more than 30 mass%. By setting the amount of the reaction substrate in such a range, a polyamic acid resin can be obtained at a low cost and in a high yield.

The temperature at which the tetracarboxylic dianhydride and the diamine compound are reacted is not particularly limited, but is usually 0 ° C. or higher, preferably 20 ° C. or higher. On the other hand, it is usually 100 ° C. or lower, preferably 80 ° C. or lower. The atmosphere may be air or an inert atmosphere. When the polyimide film is required to be colorless and transparent, it is preferably heated in an inert atmosphere such as nitrogen in order to suppress coloring.
The reaction time is not particularly limited, but is usually 1 hour or longer, preferably 2 hours or longer, and is usually 100 hours or shorter, preferably 24 hours or shorter. By performing the reaction under such conditions, a polyamic acid resin can be obtained at a low cost and in a high yield.

  Solvents used for the reaction with tetracarboxylic dianhydride and diamine compound include hydrocarbon solvents such as hexane, cyclohexane, heptane, benzene, toluene, xylene and mesitylene; carbon tetrachloride, methylene chloride, chloroform, 1, 2 -Halogenated hydrocarbon solvents such as dichloroethane, chlorobenzene, dichlorobenzene and fluorobenzene; ether solvents such as diethyl ether, tetrahydrofuran, 1,4-dioxane and methoxybenzene; ketone solvents such as acetone and methyl ethyl ketone; N, N- Amide solvents such as dimethylformamide, N, N-dimethylacetamide and N-methyl-2-pyrrolidone; aprotic polar solvents such as dimethylsulfoxide and γ-butyrolactone; pyridine, picoline, rutile Emissions, heterocyclic solvents such as quinoline and isoquinoline; phenolic solvents such as phenol and cresol, but the like, but is not particularly limited. As the solvent, one kind of substance can be used, or two or more kinds of substances can be mixed and used.

  The polyamic acid resin or polyamic acid ester resin obtained by reacting the tetracarboxylic dianhydride and the diamine compound is dissolved in the solvent described above, or the tetracarboxylic dianhydride and the diamine compound By leaving it dissolved in the solvent used for the reaction, it can be used as the polyamic acid resin solution used in the present invention.

  The polyamic acid resin solution of the present invention mainly includes a repeating unit represented by the following general formula (5), (6), or (7). The abundance ratio of general formula (5) to general formula (7) in the polyamic acid resin solution of the present invention is not particularly limited.

In the general formulas (5), (6) and (7), R ¹⁰ , R ¹⁴ and R ¹⁸ are each independently synonymous with R ³ in the general formula (8) described later, and may be included. Substituents and preferred groups are also synonymous. R ¹¹ , R ¹⁵ and R ¹⁹ are each independently synonymous with R ^{4 in} formula (8), and the substituents and preferred groups that may be present are also synonymous.

R ¹² , R ¹³ , R ¹⁶ , R ¹⁷ , R ²⁰ and R ²¹ represent a hydrogen atom or an alkyl group having 1 to 14 carbon atoms which may have a substituent. Although there is no special limitation as an alkyl group, Usually, it is a C1-C14 alkyl group, a C1-C10 alkyl group is preferable, a methyl group, an ethyl group, n-propyl group, isopropyl group, n -A butyl group or an isobutyl group is more preferable, and a methyl group or an ethyl group is still more preferable. Examples of the substituent that the alkyl group may have include a halogen atom.

<Polyimide resin solution manufacturing method>
The polyimide resin contained in the polyimide resin solution used in the present invention is obtained by subjecting a polyamic acid resin or a polyamic acid ester resin to dehydration cyclization or dealcoholization cyclization in the presence of a solvent, and a tetracarboxylic dianhydride and a diisocyanate compound. It is obtained by a method of reacting in the presence of a solvent (hereinafter collectively referred to as imidization).

  The imidization method is not particularly limited, and can be performed using any conventionally known method. Examples thereof include thermal imidization that causes thermal cyclization and chemical imidization that causes chemical cyclization. These imidization reactions may be used alone or in combination. Hereinafter, an example of the imidization method will be described, but the present invention is not limited to this method.

<Heated imide>
The method for heat imidization in the solution will be described below.
The polyimide resin solution can be obtained by heating a polyamic acid resin or a polyamic acid ester resin in the presence of a solvent, or heating a tetracarboxylic dianhydride and a diisocyanate compound in the presence of a solvent.
When the polyamic acid resin or the polyamic acid ester resin is heated in the presence of a solvent, it is preferable that water or alcohol generated by imidization is discharged out of the reaction system in order to inhibit the ring closure reaction. For example, a method in which water is discharged out of the system by azeotropically boiling an organic solvent such as toluene or xylene with water is often used.

  Examples of the solvent used when imidizing by heating include a solvent used in the reaction for obtaining the polyamic acid resin or the polyamic acid ester resin. Among them, amide solvents such as N, N-dimethylformamide, N, N-dimethylacetamide and N-methyl-2-pyrrolidone are highly soluble in polyamic acid resin, polyamic acid ester resin and polyimide resin, and have a boiling point. This is preferable because the imidization reaction proceeds efficiently.

  When the polyamic acid resin or the polyamic acid ester resin is heated in the presence of a solvent, the concentration of the polyamic acid resin or the polyamic acid ester resin in the imidization reaction solution is not particularly limited. Usually, it is 5% by mass or more, preferably 10% by mass or more, and more preferably 20% by mass or more. Moreover, it is 80 mass% or less normally, Preferably it is 60 mass% or less, More preferably, it is 40 mass% or less. 20 mass% or more is preferable in terms of high production efficiency, and 40 mass% or less is preferable in that the solution viscosity is easy to handle with ordinary production equipment.

  When the tetracarboxylic dianhydride and the diisocyanate compound are heated in the presence of a solvent, the amounts of the tetracarboxylic dianhydride and the diisocyanate compound in the imidization reaction solution are not particularly limited. For example, the total weight of the tetracarboxylic dianhydride and the diisocyanate compound is not particularly limited, but is usually 1% by mass or more, preferably 5% by mass or more, based on the amount of the imidization reaction solution, Usually, it is 70 mass% or less, Preferably it is 30 mass% or less. By setting it in such a range, the solution viscosity is good in yield and easy to handle with ordinary production equipment.

  The imidation reaction temperature is not particularly limited, but is usually 50 ° C or higher, preferably 80 ° C or higher, more preferably 120 ° C or higher, and usually 300 ° C or lower, preferably 280 ° C or lower, more preferably 250 ° C or lower. . It is preferable in that the imidization reaction proceeds efficiently when the temperature is 120 ° C or higher, and it is preferable in that the side reaction other than the imidization reaction is suppressed when the temperature is 250 ° C or lower. The pressure during the reaction may be normal pressure, increased pressure, or reduced pressure. The atmosphere may be air or an inert atmosphere. When the polyimide film is required to be colorless and transparent, it is preferably heated in an inert atmosphere such as nitrogen in order to suppress coloring.

  Moreover, tertiary amines etc. can also be added as a catalyst which accelerates | stimulates imidation. Specifically, trimethylamine, triethylamine, tripropylamine, tributylamine, tritanolamine, N, N-dimethylethanolamine, N, N-diethylethanolamine, triethylenediamine, N-methylpyrrolidine, N-ethylpyrrolidine, N- Methylpiperidine, N-ethylpiperidine, imidazole, pyridine, quinoline, isoquinoline, and the like can be used as a catalyst. The amount of the catalyst used is preferably from 0.1 to 100 mol%, more preferably from 1 to 10 mol%, based on the carboxyl group or ester group. When the amount of the catalyst used is in such a range, the reaction can be performed at a low cost and with a high yield.

<Chemical imidization>
The case where chemical imidation is used as the imidation method will be described below. The chemical imidization of the present invention refers to heating a polyamic acid by adding a dehydrating condensing agent in the presence of a solvent.
Examples of the solvent used when imidizing the polyamic acid resin or the polyamic acid ester resin include those used in the heating imidization.

  Although there is no restriction | limiting in particular in the density | concentration of the polyamic acid resin or polyamic acid ester resin of an imidation reaction solution, Usually, 5 mass% or more, Preferably it is 10 mass% or more, More preferably, it is 20 mass% or more. Moreover, it is 80 mass% or less normally, Preferably it is 60 mass% or less, More preferably, it is 40 mass% or less. 20% by mass or more is preferable in terms of high production efficiency, and 40% or less is preferable in that the solution viscosity is easy to handle in normal production equipment.

The imidation reaction temperature is not particularly limited, but is usually 50 ° C or higher, preferably 80 ° C or higher, more preferably 120 ° C or higher, and usually 300 ° C or lower, preferably 280 ° C or lower, more preferably 250 ° C or lower. . It is preferable in that the imidization reaction proceeds efficiently when the temperature is 120 ° C or higher, and it is preferable in that the side reaction other than the imidization reaction is suppressed when the temperature is 250 ° C or lower. The pressure during the reaction may be normal pressure, increased pressure, or reduced pressure. The atmosphere may be air or an inert atmosphere. When the polyimide film is required to be colorless and transparent, it is preferably heated in an inert atmosphere such as nitrogen in order to suppress coloring.
Further, a tertiary amine or the like can be added as a catalyst for promoting imidization in the same manner as in the heating imidization.

  N, N-2-substituted carbodiimide such as N, N-dicyclohexylcarbodiimide or N, N-diphenylcarbodiimide; acid anhydride such as acetic anhydride or trifluoroacetic anhydride; chloride such as thionyl chloride or tosyl chloride Acetyl chloride, acetyl bromide, propionyl iodide, acetyl fluoride, propionyl chloride, propionyl bromide, propionyl iodide, propionyl fluoride, isobutyryl chloride, isobutyryl bromide, isobutyryl iodide, isobutyryl fluoride Ride, n-butyryl chloride, n-butyryl bromide, n-butyryl iodide, n-butyryl fluoride, mono-, di-, tri-chloroacetyl chloride, mono-, di-, tri- Lomoacetyl chloride, mono-, di-, tri-iodoacetyl chloride, mono-, di-, tri-fluoroacetyl chloride, chloroacetic anhydride, phenylphosphonic dichloride, thionyl chloride, thionyl bromide, thionyl iodide or thionyl fluoride Halide compounds such as rides; phosphorus compounds such as phosphorus trichloride, triphenyl phosphite or diethyl phosphate anide can be added.

  The amount of these dehydrating condensing agents to be used is usually 0.5 mol, preferably 1 mol or more, and usually 20 mol or less, preferably 10 mol or less, relative to 1 mol of the polyamic acid resin or polyamic acid ester resin skeleton. These can be used alone or in combination of two or more.

  Moreover, the polyamic acid resin and the polyimide resin in the polyamic acid resin solution and the polyimide resin solution used in the present invention may be end-capped as necessary. By end-capping, the polymerizability of each resin end is lowered, and the solution viscosity of the polyamic acid resin solution and the polyimide resin solution is preferable.

The terminal sealing method is not limited, and any conventionally known method may be used. You may seal in any step which prepares a polyamic acid resin solution and a polyimide resin solution.
A preferable method includes a method using a terminal blocking agent. For example, when sealing is performed using a terminal sealing agent, any conventionally known terminal sealing agent may be used. For example, as the terminal blocking agent for sealing the terminal amino group, phthalic anhydride, 1,2-cyclohexanedicarboxylic anhydride, 4-methylcyclohexane-1,2-dicarboxylic anhydride or (2-methyl -2-propenyl) acid anhydrides such as succinic anhydride; organic acid chlorides such as benzoic acid chloride. In addition, examples of the terminal blocking agent for sealing the terminal acid anhydride group include amine compounds such as 3-aminophenylacetylene, aniline, and cyclohexylamine.

  The concentration of the polyimide resin in the polyimide resin solution used in the present invention is not particularly limited, but is usually 1% by mass or more, preferably 5% by mass or more. Moreover, it is 80 mass% or less normally, Preferably it is 50 mass% or less. By adjusting the concentration of the polyimide resin in the solution within this range, an extreme increase in viscosity during the reaction can be suppressed, and good workability can be achieved.

Although there is no special restriction | limiting, the viscosity of the polyimide resin solution used for this invention is 10 mPa * s or more normally, Preferably it is 1.0 * 10 < ² > mPa * s or more. Moreover, it is 5.0 * 10 < ⁴ > mPa * s or less normally, Preferably it is 2.0 * 10 < ⁴ > mPa * s or less. By adjusting the viscosity of the polyimide resin solution within the above range, when the polyimide resin solution is applied and the polyimide film layer is formed, solvent removal (drying) tends to be facilitated.

The viscosity of the polyimide resin solution is measured at 25 ° C. using an E-type viscometer. The viscosity can be measured by a known method, for example, according to the method described in International Publication No. 99/60622.
The polyimide resin solution of the present invention may have an unreacted polyamic acid resin or polyamic acid ester resin. The ratio of the polyamic acid resin or the polyamic acid ester resin in the polyimide resin solution is not particularly limited, but is usually 30% by mass or less, preferably 20% by mass or less, and more preferably 10% by mass or less. When more than 30% by mass of the polyamic acid resin or the polyamic acid ester resin is contained in the polyimide resin solution, the polyimide resin and the polyamic acid resin or the polyamic acid ester resin may be phase-separated to cause white turbidity. Moreover, when the polyimide film obtained from the polyimide resin solution which phase-separated heterogeneously needs colorless transparency, colorless transparency may become low.

The ratio of the polyamic acid resin or the polyamic acid ester resin to the polyimide resin in the polyimide resin solution is represented by the following formula.
Ratio of polyamic acid resin or polyamic acid ester resin in polyimide resin solution to polyimide resin = (substance amount of polyamic acid resin or polyamic acid ester resin in polyimide resin solution) / (polyamic acid resin or polyamic acid in polyimide resin solution) Substance amount of ester resin + substance amount of polyimide resin in polyimide resin solution) × 100

  The substance amount of the polyamic acid resin or polyamic acid ester resin in the polyimide resin solution is the weight of the polyamic acid resin or polyamic acid ester resin component contained in the polyimide resin solution represented by the general formulas (5), (6) and (7 ) Divided by the average molecular weight of each structure represented.

  The substance amount of the polyimide resin in the polyimide resin solution is obtained by dividing the weight of the polyamic acid resin or polyamic acid ester resin component contained in the polyimide resin solution by the molecular weight of the structure represented by the general formula (8) described later. Desired. Various methods for measuring the amount of polyamic acid resin or polyamic acid ester resin in polyimide resin solution are known, including nuclear magnetic resonance spectroscopy (NMR), Fourier transform infrared spectroscopy (FT-IR method), and imide ring closure. Quantitative determination of water content, method of neutralization titration of carboxylic acid contained in polyamic acid (see JP 2009-269958 A), measurement of luminescence intensity or absorption intensity by labeling specific functional groups (See Japanese Patent No. 4529760).

  As for the solvent used for the said polyimide resin solution, the solvent used at the time of reaction which obtains the polyamic acid resin or polyamic acid ester resin mentioned above is mentioned. Among them, amide solvents such as N, N-dimethylformamide, N, N-dimethylacetamide and N-methyl-2-pyrrolidone are highly soluble in polyamic acid resin, polyamic acid ester resin and polyimide resin, and have a boiling point. This is preferable because the imidization reaction proceeds efficiently.

  Moreover, the polyamic acid resin solution and the polyimide resin solution of the present invention may contain an antioxidant. The step of adding the antioxidant is not particularly limited, but a method of adding the antioxidant to the polyimide resin solution or the polyamic acid resin solution and using it as a solution can be suitably used. When an antioxidant is added to a polyimide resin solution or a polyamic acid resin solution, it is preferable in that it can suppress both discoloration and physical properties of the film during film formation and drying, and coloration with time of the obtained film.

The addition amount of the antioxidant is not particularly limited, but is generally preferably 0.001% by mass or more, more preferably 0.005% by mass or more, still more preferably 0.01% by mass or more, and 0.05% by mass with respect to the polyimide resin or polyamic acid resin. The above is particularly preferable. On the other hand, it is preferably 10% by mass or less, more preferably 5% by mass or less, further preferably 3% by mass or less, and particularly preferably 1% by mass or less. By being in these ranges, coloring due to deterioration of the antioxidant is suppressed, aggregation and sedimentation in the liquid resin composition is suppressed, and handling properties during coating work are excellent. There exists a tendency for it to become a molding with good smoothness and color.
Specific examples of the antioxidant include hindered phenol antioxidants, phosphorus antioxidants, sulfur antioxidants, hydroxylamine antioxidants, and the like.

(Hindered phenolic antioxidant)
Examples of the hindered phenol antioxidant include pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], N, N′-hexamethylenebis [3- ( 3,5-di-tert-butyl-4-hydroxyphenyl) propanamide], 1,2-bis (3,5-di-tert-butyl-4-hydroxycinnamoyl) hydrazine, triethylene glycol-bis [3 -(3-t-butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol-bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5-di-t-butylanilino) -1,3,5-triazine, thiodiethylenebis [3- ( , 5-di-t-butyl-4-hydroxyphenyl) propionate], 2-thio-diethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], octadecyl-3- ( 3,5-di-t-butyl-4-hydroxyphenyl) propionate, N, N′-hexamethylenebis (3,5-di-t-butyl-4-hydroxy-hydrocinnamamide), 3,5- Di-t-butyl-4-hydroxybenzylphosphonate-diethyl ester, 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, Tris- (3,5-di-tert-butyl-4-hydroxybenzyl) -isocyanurate, 2,4, -bis [(octylthio) methyl] -o-cresol, isooctane Ru-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 2-tert-butyl-6- (3-tert-butyl-2-hydroxy-5-methylbenzyl) -4-methyl Phenyl acrylate, 2- [1- (2-hydroxy-3,5-di-t-pentylphenyl) ethyl] -4,6-di-t-pentylphenyl acrylate, 2,2′-methylenebis (6-t- Butyl-4-methylphenol), 4,4′-butylidenebis (6-tert-butyl-3-methylphenol), 4,4′-thiobis (6-tert-butyl-3-methylphenol), 3,9- Bis [2- [3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5.5 ] Undeca 1,3,5-tris [[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] -1,3,5-triazine-2,4,6 (1H, 3H , 5H) -trione, 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propion Acid stearyl, bis [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionic acid] [ethylenebis (oxyethylene)], 3- (1,1-dimethylethyl) -4-hydroxy- 5-methyl-benzenepropanoic acid-2,4,8,10-tetraoxaspiro [5,5] undecane-3,9-diylbis (2,2-dimethyl-2,1-ethanediyl) ester 2,4, Examples include 6-tris (3 ′, 5′-di-t-butyl-4′-hydroxybenzyl) mesitylene. .

(Phosphorus antioxidant)
The phosphorus antioxidant may be an inorganic compound or an organic compound, and is not particularly limited. Preferred phosphorus compounds include inorganic phosphates such as monosodium phosphate, disodium phosphate, trisodium phosphate, sodium phosphite, calcium phosphite, magnesium phosphite, manganese phosphite, and triphenyl phosphite. , Trioctadecyl phosphite, tridecyl phosphite, trinonylphenyl phosphite, diphenylisodecyl phosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, tetra (tridecyl- 4,4′-isopropylidene diphenyl diphosphite, 2,2-methylenebis (4,6-di-tert-butylphenyl) octyl phosphite, tris (2,4-di-tert-butylphenyl) phosphite, tris (Isodecyl) Phosphi , Tris (tridecyl) phosphite, phenyl diisooctyl phosphite, phenyl diisodecyl phosphite, phenyl di (tridecyl) phosphite, diphenyl isooctyl phosphite, diphenyl isodecyl phosphite, diphenyl tridecyl phosphite, phosphonic acid [ 1,1-diphenyl-4,4′-diylbistetrakis-2,4-bis (1,1-dimethylethyl) phenyl] ester, triphenyl phosphite, tris (nonylphenyl) phosphite, 4,4′- Isopropylidene diphenol alkyl phosphite, tris (biphenyl) phosphite, distearyl pentaerythritol diphosphite, di (2,4-di-t-butylphenyl) pentaerythritol diphosphite Sulphite, di (nonylphenyl) pentaerythritol diphosphite, phenylbisphenol A pentaerythritol diphosphite, tetra (tridecyl) -4,4'-butylidenebis (3-methyl-6-t-butylphenol) diphosphite, hexa ( Tridecyl) -1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane triphosphite, 3,5-di-tert-butyl-4-hydroxybenzyl phosphate diethyl ester, Sodium-bis (4-t-butylphenyl) phosphate, sodium-2,2'-methylene-bis (4,6-di-t-butylphenyl) phosphate, 1,3-bis (diphenoxyphosphoryl) Oxy) benzene, 3,9-bis (2,4-di-t-butyl) Phenoxy) -2,4,8,10-tetraoxa-3,9-diphosphaspiro [5.5] undecane, 2,4,8,10-tetrakis (1,1-dimethylethyl) -6-[(2-ethylhexyl) ) Oxy] -12H-dibenzo [1,3,2] dioxaphosphocine, tris (2,4-di-t-butylphenyl) phosphite, tris (monononylphenyl) phosphite, tris (dinonylphenyl) ) Phosphite, tris (4-nonylphenyl) phosphite, phosphorous acid (1-methylethylidene) di-4,1-phenylenetetra-c12-15-alkyl ester, diphenyl phosphite (2-ethylhexyl), etc. And organic phosphorus secondary antioxidants.

(Sulfur-based antioxidant)
Examples of the sulfur-based antioxidant include dioctadecyl 3,3′-thiodipropionate 3,3′-thiodipropionate didodecyl, dilauryl-3,3′-thiodipropionate, lauryl thiodithionate, Ditridecyl-3,3'-thiodipropionate, dimyristyl-3,3'-thiodipropionate, distearyl-3,3'-thiodipropionate, tetrakis-methylene-3-laurylthiopropionate methane, Distearyl-3,3′-methyl-3,3′-thiodipropionate, laurylstearyl-3,3′-thiodipropionate, bis [2-methyl-4- (3-n-alkylthiopropionyloxy) -5-tert-butylphenyl] sulfide, β-lauryl thiopropionate, 2-mercaptobenzimidazole, 2-methyl Capto-5-methylbenzimidazole, bis [3- (dodecylthio) propionic acid] 2,2-bis [[3- (dodecylthio) -1-oxopropyloxy] methyl] -1,3-propanediyl, bis [3 -(Dodecylthio) propanoic acid] thiobis [2- (1,1-dimethylethyl) -5-methyl-4,1-phenylene] and the like.

(Hydroxylamine antioxidant)
Examples of the hydroxylamine antioxidant include dialkylamines such as dioctadecylhydroxylamine, N, O-dialkylhydroxylamine, 1-naphthohydroxamic acid, 4,5-dibromo-N-methoxy-N-methyl-2- Furan carboxamide, 4- (hydroxyamino) quinoline N-oxide, acetohydroxamic acid, benzenesulfohydroxamic acid, benzohydroxamic acid, hydroxyurea, L-canavanine sulfate hydrate, N, N'-dimethoxy-N, N'- Dimethyloxamide, N, N, O-triacetylhydroxylamine, N, N, O-tris (trimethylsilyl) hydroxylamine, N, N-dibenzylhydroxylamine, N, N-diethylhydroxylamine, N, O-bis (Trifluoroacetyl) hydride Roxylamine, N, O-bis (trimethylsilyl) hydroxylamine, N, O-dimethylhydroxylamine hydrochloride, N- (diethylcarbamoyl) -N-methoxyformamide, N- (tert-butyl) hydroxylamine hydrochloride, N-benzoyl -N-phenylhydroxylamine, N-carbobenzoxyhydroxylamine, N-cinnamoyl-N- (2,3-xylyl) hydroxylamine, N-hydroxyurethane, N-methoxy-N, O-bis (trimethylsilyl) carbamate, N-methoxy-N-methyl-2-furancarboxamide, N-methoxy-N-methylacetamide, N-methoxydiacetamide, N-methyl-2-dimethylaminoacetohydroxamic acid, N-methyl-N, O-bis ( Trimethylsilyl) bi Roxylamine, N-methyl furohydroxamic acid, N-methylhydroxylamine hydrochloride, octanohydroxamic acid, salicylhydroxamic acid, sodium benzohydroxamic acid hydrate, sodium octanohydroxamic acid hydrate, N- (benzyloxy) carbamine Tert-butyl acid, tert-butyl N-hydroxycarbamate, tert-butyl [bis (4-methoxyphenyl) phosphinyloxy] carbamate, 4,5-dibromo-N-methoxy-N-methyl-2-furan Carboxamide, carboxymethoxylamine hemihydrochloride, hydroxylamine-O-sulfonic acid, L-canavanine sulfate hydrate, N, N'-dimethoxy-N, N'-dimethyloxamide, N, N, O-triacetylhydroxyl Amine, N, N, O-to (Trimethylsilyl) hydroxylamine, N, O-bis (trifluoroacetyl) hydroxylamine, N, O-bis (trimethylsilyl) hydroxylamine, N, O-dimethylhydroxylamine hydrochloride, N- (diethylcarbamoyl) -N- Methoxyformamide, N-methoxy-N, O-bis (trimethylsilyl) carbamate, N-methoxy-N-methyl-2-furancarboxamide, N-methoxy-N-methylacetamide, N-methoxydiacetamide, N-methyl-N , O-bis (trimethylsilyl) bidoxylamine, O- (2,3,4,5,6-pentafluorobenzyl) hydroxylamine hydrochloride, O- (2-trimethylsilylethyl) hydroxylamine hydrochloride, O- (trimethylsilyl) ) Hydroxyla , O-4-nitrobenzylhydroxylamine hydrochloride, O-allylhydroxylamine hydrochloride, O-benzylhydroxylamine hydrochloride, O-isobutylhydroxylamine hydrochloride, O-methylhydroxylamine hydrochloride, N- (benzyloxy ) Tert-butyl carbamate, [bis (4-methoxyphenyl) phosphinyloxy] carbamate tert-butyl and the like.

Among the antioxidants, hindered phenol compounds and phosphorus antioxidants are preferable in that they have excellent compatibility with polyimide resin solutions and polyamic acid resin solutions, and can effectively suppress coloring.
Among the above hindered phenol compounds, N, N′-hexamethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propanamide] (trade name IRGANOX1098 manufactured by BASF), pentaerythritol Tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] (trade name IRGANOX 1010 manufactured by BASF) 1,2-bis (3,5-di-t-butyl-4- Hydroxycinnamoyl) hydrazine (trade name IRGANOX MD1024, manufactured by BASF), bis [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionic acid] [ethylenebis (oxyethylene)] (BASF Product name IRGANOX 245) is preferred.
Of the phosphorus-based antioxidants, tris (2,4-di-t-butylphenyl) phosphite (trade name IRGAFOS 168 manufactured by BASF) is preferable.
These antioxidants are excellent in compatibility with the polyimide resin solution and the polyamic acid resin solution, and tend to effectively suppress coloring. In addition, there is a tendency that agglomeration and sedimentation in the solution is suppressed, a handling property during coating work is excellent, and a molded article having a good surface smoothness is obtained, and an antioxidant from the polyimide film layer. This is preferable in that the bleeding out can be suppressed.

The above-mentioned antioxidants may be used alone or in combination of two or more, but when they are mixed, a mixture of hindered phenolic antioxidants and phosphorus antioxidants or hindered phenolic antioxidants A mixture of an agent and a sulfur-based antioxidant is preferred.
When using a mixture of hindered phenolic antioxidant and phosphorus antioxidant, among others, N, N′-hexamethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propanamide ] (Trade name IRGANOX 1098 manufactured by BASF) and tris (2,4-di-t-butylphenyl) phosphite (trade name IRGAFOS 168 manufactured by BASF); pentaerythritol tetrakis [3- (3,5 -Di-t-butyl-4-hydroxyphenyl) propionate] (trade name IRGANOX 1010 manufactured by BASF) and tris (2,4-di-t-butylphenyl) phosphite (trade name IRGAFOS 168 manufactured by BASF) 1,2-bis (3,5-di-t-butyl-4-hydroxycinnamoyl) hydrazine (trade name IRGANOX MD1024, manufactured by BASF) and tris (2,4-di-t-butyl) Ruphenyl) phosphite (trade name IRGAFOS 168 manufactured by BASF); bis [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propanoic acid] [ethylenebis (oxyethylene)] (BASF A mixture of trade name IRGANOX 245) manufactured by the company and tris (2,4-di-t-butylphenyl) phosphite (trade name IRGAFOS 168 manufactured by BASF); compatibility with polyimide resin solution and polyamic acid resin solution It is preferable at the point which is excellent in it and can suppress coloring effectively.

  When using a mixture of a hindered phenolic antioxidant and a sulfurous antioxidant, among others, N, N′-hexamethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propanamide ] (Trade name IRGANOX 1098 manufactured by BASF) and dioctadecyl 3,3′-thiodipropionate (trade name IRGANOX PS 802 manufactured by BASF); pentaerythritol tetrakis [3- (3,5-di- (t-butyl-4-hydroxyphenyl) propionate] (trade name IRGANOX 1010, manufactured by BASF) and dioctadecyl 3,3′-thiodipropionate (trade name IRGANOX PS 802, manufactured by BASF); 1,2- Bis (3,5-di-t-butyl-4-hydroxycinnamoyl) hydrazine (trade name IRGANOX MD1024, manufactured by BASF) and dioctadecyl 3,4′-thiodipropionate (BA) Mixture with trade name IRGANOX PS 802 manufactured by F company; bis [3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionic acid] [ethylene bis (oxyethylene)] (trade name, manufactured by BASF A mixture of IRGANOX 245) and dioctadecyl 3,3′-thiodipropionate (trade name IRGANOX PS 802, manufactured by BASF); excellent compatibility with polyimide resin solutions and polyamic acid resin solutions, and effective coloring It is preferable at the point which can be suppressed. Moreover, the mixing ratio at the time of mixing is not specifically limited.

  Further, in addition to the above antioxidants, various additives usually used in resin compositions, for example, lubricants, colorants, stabilizers, ultraviolet absorbers, antistatic agents, flame retardants, plasticizers or mold release, as desired. You may mix | blend an agent, a leveling agent, surfactant, an antifoamer, etc. with the polyimide resin solution and / or polyamic acid resin solution which concern on this embodiment. These various fillers and additive components may be added at any stage of any process for producing the polyimide resin solution and the polyamic acid resin solution. In addition, it is also possible to mix | blend various additives with respect to the polyamic acid resin solution and / or polyimide resin solution which concern on this embodiment as needed. For example, an inorganic filler or an organic filler such as powder, granule, plate, or fiber can be blended within a range that does not impair the object of the invention.

  Examples of inorganic fillers include oxides such as silica, diatomaceous earth, barium ferrite, beryllium oxide, pumice or pumice balloon; hydroxides such as aluminum hydroxide, magnesium hydroxide or basic magnesium carbonate; calcium carbonate, Carbonates such as magnesium carbonate, dolomite or dosonite; sulfates and sulfites such as calcium sulfate, barium sulfate, ammonium sulfate or calcium sulfite; talc, clay, mica, asbestos, glass fiber, glass balloon, glass beads, calcium silicate, Silicates such as montmorillonite or bentonite; carbons such as carbon fiber, carbon black, graphite or carbon hollow sphere; molybdenum sulfide, zinc borate, barium metaborate, calcium borate, sodium borate or boron Powder-like, granular, plate-like, or fibrous inorganic fillers such as fibers; Powder-like, granular, fibrous, or whisker-like metal fillers such as metal elements, metal compounds, and alloys; silicon carbide, silicon nitride, Examples thereof include powder fillers such as zirconia, aluminum nitride, titanium carbide, and potassium titanate, granular, fibrous, or whisker-like ceramic fillers.

On the other hand, examples of organic fillers include shell fibers such as fir shells, carbon nanotubes, fullerenes, wood flour, cotton, jute, paper strips, cellophane pieces, aromatic polyamide fibers, cellulose fibers, nylon fibers, polyester fibers, Examples thereof include polypropylene fiber, thermosetting resin powder, and rubber.
As a filler, what was processed into flat form, such as a nonwoven fabric, may be used, and a plurality of materials may be mixed and used. Furthermore, as desired, various additives commonly used in resin compositions, such as lubricants, colorants, stabilizers, antioxidants, ultraviolet absorbers, antistatic agents, flame retardants, plasticizers or mold release agents, are added. The polyamic acid resin solution and / or the polyimide resin solution according to this embodiment may be blended. These various fillers and additive components may be added at any stage of any process for producing a polyamic acid resin solution and / or a polyimide resin solution.

<Polyimide film layer>
Hereinafter, the polyimide film layer obtained in the process of providing a polyimide film layer by applying a polyamic acid resin solution and / or a polyimide resin solution on a silane coupling layer provided on the carrier substrate surface and drying it will be described.

  The production method of the present invention includes a step of providing a polyimide film layer by applying and drying a polyamic acid resin solution and / or a polyimide resin solution on a silane coupling layer provided on the surface of a carrier substrate. A polyimide film layer obtained by this method can be distinguished from a polyimide film (laminated body or device film) produced by heating and pressing the polyimide film and affixing it to the carrier substrate. As a method of distinguishing, a method of analyzing an interface between a silane coupling layer and a glass and / or an interface between a polyimide film and a silane coupling layer, a method of analyzing a polyimide film, a method of analyzing a solution in which a polyimide film is dissolved in a solvent Etc.

  The analysis method is not particularly limited, but X-ray photoelectron spectroscopy (ESCA), infrared spectroscopy (IR), analysis using a distributed X-ray analyzer (SEM-EDX), scanning electron microscope (SEM) Analytical methods using TEM, transmission electron microscope (TEM), optical microscope, birefringence measuring device, atomic force microscope (AFM), elemental analysis and nuclear magnetic resonance (NMR), liquid chromatography (LC), gas chromatography Examples of the method include chromatography (GC), mass spectrometry, or a combination thereof. Laminates and device films with different manufacturing methods may differ in the type and amount of functional groups on the surface or the compounds remaining on the surface, the shape of the surface, the orientation of the polymer forming the film, etc. Can be determined.

  The coefficient of thermal expansion of the polyimide film layer is preferably 100 ppm / K or less, more preferably 70 ppm / K or less in the range of 100 to 200 ° C., and most preferably the same thermal expansion as the carrier substrate. preferable. When the coefficient of thermal expansion is in such a range, peeling of the polyimide film layer from the carrier substrate due to a temperature change in a process for producing a device provided on the polyimide film layer tends to be prevented.

The polyimide film layer is preferably less colored and heat resistant, and preferably has high mechanical strength. Moreover, it is preferable to have colorless transparency as needed. In the present specification, being colorless and transparent means that when it is molded into a desired shape, the transmittance of light of 400 nm is usually 60% or more, preferably 70% or more, particularly preferably 80% or more. Say something. A polyimide film layer having a high light transmittance is suitably used in a device that requires translucency, such as a photoelectric conversion element.
In this specification, the total light transmittance at 400 nm according to JIS K 7136-1 is used as the transmittance.

  When colorless transparency is required for the polyimide film forming the polyimide film layer, the yellowness (yellow index (YI)) when the film thickness is 50 ± 5 μm is usually −10 or more, preferably −5 or more, More preferably, it is −1 or more. On the other hand, it is usually 20 or less, preferably 15 or less, more preferably 10 or less, and still more preferably 5 or less.

The polyimide film layer preferably has a glass transition temperature (Tg) of 150 ° C. or higher, more preferably 200 ° C. or higher, more preferably 250 ° C. or higher. When the glass transition temperature is high, the thermal effect on the device provided on the polyimide film layer is lowered, and the heat resistance tends to be improved.
The polyimide film layer depends on the type of device provided on the layer and the application, but preferably has the following mechanical strength.
Although there is no special restriction | limiting, the tensile strength of the polyimide film layer obtained in this embodiment is 50 Mpa or more normally, Preferably it is 70 Mpa or more, on the other hand, it is 400 Mpa or less normally, Preferably it is 300 Mpa or less. The tensile elastic modulus is not particularly limited, but is usually 1000 MPa or more, preferably 1500 MPa, and is usually 20 Gpa or less, preferably 10 Gpa or less.
Further, the tensile elongation is not particularly limited, but is usually 10% GL or more, preferably 20% GL, and is usually 300% GL or less, preferably 200% GL or less.
When the polyimide film layer has such mechanical strength, a more durable device can be obtained.

  The polyimide film layer used in the present invention has a structure represented by the following general formula (8).

[In general formula (8), R ³ represents a tetravalent organic group,
R ⁴ represents a divalent organic group,
n represents an integer of 1 or more, and when n is 2 or more, a plurality of R ³ and R ⁴ present in one molecule of the structure represented by the general formula (8) may be the same or different. . ]

n is an integer of 1 or more, and the upper limit is not particularly limited as long as the effect of the present invention is not impaired, but the weight average molecular weight of the polyimide film layer represented by the general formula (8) is preferably 20000 or more, and more preferably. From the viewpoint of the toughness of the polyimide film layer, it is preferable to determine n so that it becomes 40,000 or more.
In addition, since the polyimide film layer of the present invention includes a plurality of structures represented by the general formula (8), a plurality of tetravalent organic groups R ³ and a plurality of divalent organic groups R ⁴ are included. Here, the plurality of tetravalent organic groups R ³ and the plurality of divalent organic groups R ⁴ may all have the same structure or different structures.

R ³ represents a tetravalent organic group and is not particularly limited as long as it does not impair the effects of the present invention. Specifically, R ³ is a tetravalent organic group derived from tetracarboxylic dianhydride. Examples of tetracarboxylic dianhydrides include aromatic tetracarboxylic dianhydrides, aromatic tetracarboxylic dianhydrides containing fluorine groups, and aliphatic tetracarboxylic dianhydrides.

When colorless transparency is required for the polyimide film, it is preferable to use an alicyclic tetracarboxylic dianhydride residue among R ³ , and particularly a bicyclohexane skeleton represented by the general formula (9). 1,1′-bicyclohexane-3,3 ′, 4,4′-tetracarboxylic acid-3,3 ′, 4,4′-dianhydride residues composed of tetracarboxylic acid residues having It is preferable.

  A polyimide film layer composed of tetracarboxylic acid residues having a bicyclohexane skeleton is a polyimide composed of tetracarboxylic acid residues having an aromatic group such as biphenyl or a monocyclic alicyclic hydrocarbon group as a skeleton. Compared with the film layer, the effect of reducing coloring and improving solubility can be obtained. Moreover, these polyimide film layers have relatively high solubility, and the solution concentration can be freely adjusted. Furthermore, these polyimide film layers are excellent in heat resistance and colorless transparency. Moreover, it has low retardation and excellent optical properties.

If the colorless and transparent of the polyimide film layer used as the film substrate is high, it is possible to obtain a high-performance display device or a light receiving device with high photoelectric conversion efficiency. For example, it can correspond to a see-through device. In addition, when used as a device substrate for an organic EL display, a bottom emission type light extraction structure that can be easily manufactured can be adopted, so that a device for a large-sized organic EL display can be easily obtained. In addition, since it does not affect the original color of the display, a high-performance device can be obtained.
Moreover, the polyimide represented by the general formula (9) has little absorption of light having a wavelength suitable for power generation of a solar cell. Therefore, when the polyimide film layer having the structure represented by the general formula (9) is used as a device substrate on the light receiving surface side of the solar cell, it has the same layer configuration as that of a solar cell using a conventional glass substrate. However, the effect that the photoelectric conversion rate does not decrease remarkably is obtained.
In addition, since the polyimide film layer having the structure represented by the general formula (9) has less aromatic skeleton, the film itself has better durability against ultraviolet rays than the conventional aromatic polyimide film. It is preferable in a certain point.

[In general formula (9), R ⁵ represents a divalent organic group,
a represents an integer of 1 or more, and when a is 2 or more, a plurality of R ⁵ present in one molecule of the structure represented by the general formula (9) may be the same or different. ]

The divalent organic group of general formula (9) R ⁵ has the same meaning as R ⁴ of general formula (8), and the substituents and preferred examples that may be present are also synonymous.

  a is an integer of 1 or more, and there is no particular upper limit as long as the effect of the present invention is not impaired, but the mass average molecular weight of the polyimide film layer represented by the general formula (9) is preferably 20000 or more, and It is preferable from the viewpoint of the strength of the polyimide film layer that a is preferably set to 40000 or more.

  As tetracarboxylic dianhydride which is a raw material of the polyimide film layer represented by the general formula (8), 1,1′-bicyclohexane-3,3 ′, 4,4′-tetracarboxylic acid-3,3 ′ , 4,4'-dianhydride, in addition to various physical properties such as heat resistance of the polyimide film layer according to the present embodiment, and when colorless transparency is required, other properties to the extent that colorless transparency is not impaired. Tetracarboxylic dianhydride may be mixed and used as a raw material. The tetracarboxylic dianhydride to be mixed may be one type or two or more types.

<Regarding ^{R 5 R 4} and of the general formula (8) (9)>
R ⁴ and R ⁵ are not particularly limited as long as they are divalent organic groups, but specific examples include structural units obtained by removing amino groups from diamine compounds. Examples of the diamine compound include aromatic diamine compounds, aromatic diamine compounds containing a fluorine group, and aliphatic diamine compounds. Specifically, what remove | eliminated the amino group from the diamine compound quoted with the raw material of the polyamic acid resin solution and the polyimide resin solution is mentioned.

Among the above, R ⁴ and R ⁵ are not only divalent organic groups represented by the general formula (10) but also heat resistance and a tough polyimide film layer, as well as dissolution in organic solvents. It is preferable at the point which improves property. Moreover, when colorless transparency is requested | required of a polyimide film layer, colorless transparency becomes high and it is especially preferable at the point which can reduce coloring by time-dependent deterioration.

In general formula (10), ring A ²⁰ and ring A ²¹ are each independently an aromatic group that may have a substituent, an alicyclic hydrocarbon group that may have a substituent, or a substituent. A heterocyclic group which may have a group,
p and q each independently represent an integer of 0 or more and 10 or less.
X ⁴ is a direct bond, an oxygen atom, a sulfur atom, an alkylene group which may have a substituent, a sulfonyl group, a sulfinyl group, a sulfide group, a carbonyl group, an aromatic group which may have a substituent,- NH-C (= O) - group shown, -NH- group, or _{-O-C z} H 2z -O- based (z is an integer of from 1 to 5). However, neither p nor q is 0.
Y ¹⁰ and Y ¹¹ each independently represent a direct bond, an oxygen atom, a sulfur atom, an optionally substituted alkylene group, a sulfonyl group, a sulfinyl group, a sulfide group, or a carbonyl group.
When p and / or q is 2 or more, the plurality of Y ¹⁰ , Y ¹¹ , ring A ²⁰ and ring A ²¹ may be different from each other.

The aromatic groups of the ring A ²⁰ and the ring A ²¹ of the general formula (10) are not particularly limited, but each independently includes, for example, an aromatic hydrocarbon group and an aromatic heterocyclic group. Is synonymous with those listed for R ¹¹ , and the substituents that may be present are also synonymous. The aromatic hydrocarbon group for ring A ²⁰ and ring A ²¹ preferably has 6 or more carbon atoms, preferably 30 or less, and more preferably 25 or less. It exists in the tendency which can obtain the high mechanical property and heat resistance of a polyimide film layer because it is this range.
In addition, the aromatic heterocyclic group of ring A ²⁰ and ring A ²¹ preferably has 2 or more carbon atoms, more preferably 3 or more, and preferably 30 or less, and more preferably 25 or less. It exists in the tendency which can obtain the high mechanical property and heat resistance of a polyimide film layer because it is this range.
Among the aromatic groups of ring A ²⁰ and ring A ²¹ , a benzene ring, a biphenylene ring, a terphenyl ring, a benzotriazole ring, and a benzoxazole ring tend to provide high mechanical properties and heat resistance of the polyimide film layer.

The alicyclic hydrocarbon group of ring A ²⁰ and ring A ²¹ is derived from an aliphatic ring and is not particularly limited. Specific examples include those having 3 to 30 carbon atoms such as cyclobutane ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, norbornane ring, norbornene ring, hydrindane ring, decahydronaphthalene ring, adamantane ring and the like. It is done. Among these, a cyclohexane ring, a cyclopentane ring, and a norbornane ring are preferable from the viewpoint of mechanical properties and heat resistance of the polyimide film layer.

The heterocyclic group of ring A ²⁰ and ring A ²¹ does not have an unsaturated bond, and includes one or more heteroatoms in a three or more-membered ring, and is not particularly limited. Specific examples include an aziridine ring and a thiolane ring.
Examples of the substituent that the heterocyclic group of ring A ²⁰ and ring A ²¹ may have include a halogen atom, an alkyl group, an alkoxy group, and a hydroxyl group.

Regarding the aromatic group, alicyclic hydrocarbon group, or heterocyclic group that is ring A ²⁰ and ring A ²¹ , the position of bonding to Y ¹⁰ , Y ¹¹ , or X ⁴ is not particularly limited.

In the general formula (10), p and q are each independently an integer of 0 or more, preferably 1 or more, and on the other hand, an integer of 10 or less, preferably 5 or less.
In the formula (10), X ⁴ may have a direct bond, an oxygen atom, a sulfur atom, an alkylene group which may have a substituent, a sulfonyl group, a sulfinyl group, a sulfide group, a carbonyl group or a substituent. An aromatic group, —NH—C (═O) —, —NH—, or —O—C _z H _2z —O— is shown. However, z shows the integer of 1-5. Among these, from the viewpoint of high mechanical properties and heat resistance of the polyimide film, it is preferably a direct bond, an oxygen atom, an alkylene group which may have a substituent, a sulfinyl group, or a sulfonyl group, an oxygen atom, An alkylene group which may have a substituent or a sulfinyl group is particularly preferable.

The alkylene group for X ⁴ is not particularly limited, but is preferably an alkylene group having 1 to 20 carbon atoms from the viewpoint of mechanical properties and heat resistance of the polyimide film, and an alkylene group having 1 to 10 carbon atoms. More preferably. Specific examples of the alkylene group include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, and a 2,2-propanediyl group.

The aromatic group for X ⁴ is not particularly limited, and examples thereof include an aromatic hydrocarbon group and an aromatic heterocyclic group. Specifically it has the same meanings as those mentioned R ^11, is also synonymous substituent which may have. The aromatic hydrocarbon group for X ⁴ preferably has 6 or more carbon atoms, preferably 30 or less, and preferably 25 or less from the viewpoint of mechanical properties and heat resistance of the polyimide film layer.
The aromatic heterocyclic group represented by X ⁴ preferably has 2 or more carbon atoms, preferably 30 or less, and preferably 25 or less from the viewpoint of mechanical properties and heat resistance of the polyimide film layer.
Among the aromatic groups of X ^4, a phenylene group, a naphthylene group and a pyridylene group, it is particularly preferred.

Examples of the substituent that the alkylene group or aromatic group of X ⁴ may have include an alkyl group having 1 to 5 carbon atoms, a hydroxy group, an alkoxy group, an amino group, a carboxyl group, and an epoxy group. These substituents may be further substituted with a halogen atom such as a fluorine atom or a chlorine atom.

Y ¹⁰ and Y ¹¹ each independently represent a direct bond, an oxygen atom, a sulfur atom, an optionally substituted alkylene group, a sulfonyl group, a sulfinyl group, a sulfide group, or a carbonyl group. Among these, a direct bond or an oxygen atom is preferable.
When p or q is 2 or more, there are a plurality of Y ¹⁰ and Y ^{11 in} R ^{5. The} plurality of Y ¹⁰ and Y ¹¹ may have the same structure or different structures. There may be. Here, as the alkylene group which may have a substituent, the same groups as those mentioned for X ⁴ can be used.

  Among the general formula (10), a structure represented by the following general formulas (11) and (12) is particularly preferable from the viewpoint of high mechanical properties and heat resistance of the polyimide film layer.

General formula (11) corresponds to the case of p = 2 and q = 2 in general formula (10). In addition, ring A ²² and ring A ²³ in the general formula (11) have the same meaning as the ring A ²⁰ and ring A ^{24 in the} general formula (10), respectively, and the ring A ²⁵ in the general formula (11) has the general formula ( It is synonymous with the ring A ^{21 of} 10).
Further, ^{Y 12} and ^{Y 13} in the general formula (11) are respectively synonymous with ^{Y 10} and ^{Y 14} in the general formula (10), ^{Y 15} in formula (11), ^{Y 11} in the general formula (9) It is synonymous with.
Similarly to General Formula (9), Ring A ²² to Ring A ²⁵ and Y ^{12 to} Y ¹⁵ in General Formula (11) may be the same or different.

In general formula (11), ring A ²² , ring A ²³ , ring A ²⁴ and ring A ²⁵ are each independently an aromatic group which may have a substituent, and the mechanical properties of the polyimide film layer From the viewpoint of heat resistance. Among these, a phenylene group is more preferable, and a substituent that may be present is preferably a halogen atom such as a chlorine atom.
Further, from the viewpoint of mechanical properties and heat resistance of the polyimide film layer, Y ¹² and Y ¹³ are preferably a direct bond, an oxygen atom or a sulfur atom, and Y ¹⁴ and Y ¹⁵ are preferably a direct bond. .

The general formula (12) corresponds to the case where p = 1 and q = 1 in the general formula (10).
Ring A ²⁶ and ring A ²⁷ in the general formula (12) have the same meanings as the ring A ²⁰ and the ring A ^{21 in the} general formula (10), respectively. Further, ^{Y 16} and ^{Y 17} in the general formula (12) are respectively synonymous with ^{Y 10} and ^{Y 11} in the general formula (10).
In particular, from the viewpoint of mechanical properties and heat resistance of the polyimide film layer, ring A ²⁶ and ring A ²⁷ are also preferably the same structure, and Y ¹⁰ and Y ¹¹ are more preferably the same structure.

Ring A ²⁶ and Ring A ^{27 in} formula (12) each independently have an aromatic group or a substituent that may have a substituent from the viewpoint of mechanical properties and heat resistance of the polyimide film layer. An alicyclic hydrocarbon group which may be present is preferable. Among these, an aromatic group which may have a substituent is preferable, and a phenylene group is more preferable. Further, the substituent which may be present is preferably a halogen atom such as a chlorine atom.
Y ¹⁶ is preferably a direct bond, an oxygen atom or a sulfur atom from the viewpoint of mechanical properties and heat resistance of the polyimide film layer, and Y ¹⁷ is preferably a direct bond.

Among the above-mentioned, R ⁴ and R ⁵ are preferably a divalent group obtained by removing an amino group from the following compounds, from the viewpoint that heat resistance, mechanical strength and colorless transparency can be achieved simultaneously.
Specifically, 4,4′-diaminodiphenyl ether, 2,2-bis (4- (4-aminophenoxy) phenyl) propane, bis (4- (4-aminophenoxy) phenyl) sulfone, 4,4′- Diamino-2,2′-dimethylbiphenyl, N- (4-aminophenoxy) -4-aminobenzamide, 2- (4-aminophenyl) -6-aminobenzoxazole, 2- (4-aminophenyl) -5 Aminobenzoxazole, 5-amino-2- (4-aminophenyl) -1H-benzimidazole, 4,4′-methylenebis (cyclohexylamine), 2,2-bis (4- (4-aminophenoxy) phenyl) hexa Examples include fluoropropane and 4,4′-diamino-2,2′-bis (trifluoromethyl) biphenyl.

<Laminate>
The laminate of the present invention is produced by the above-described laminate production method or the like, and is a laminate having a silane coupling layer between a carrier substrate and a polyimide film layer. The silane coupling layer includes a functional group derived from the silane coupling agent represented by the general formulas (1) to (3), and the polyimide film layer has a structure represented by the general formula (8). It is preferable that the polyimide film layer is easily peeled from the carrier substrate.
Moreover, when colorless transparency is requested | required of a polyimide film layer, it is still more preferable to have a structure represented by General formula (9). With these layer configurations, the polyimide film layer can be easily peeled off from the carrier substrate, and transparency as a laminate and high durability against ultraviolet rays tend to be obtained.
Furthermore, a device can be formed on the laminate of the present invention by forming a device as shown in the method for producing a laminate. Moreover, a device film can be obtained by peeling the carrier substrate from the device laminate.

  EXAMPLES Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited to these examples. The following measurements in the examples were performed according to the following methods.

[Peel strength measurement]
The peel strength in the examples was evaluated according to a 180 degree peel test method according to JIS K 6854-2. The measurement was carried out under the following conditions.
Device name: Single column type tensile and compression testing machine STA-1225 (manufactured by A & D Corporation)
Measurement temperature and humidity: 23 ° C, 50% RH
Peeling speed: 100mm / min
Atmosphere: Air measurement Sample width: 25mm
However, a 50 mm wide Lami-off recycled paper craft tape No. 3105 (made by Nichiban Co., Ltd.) is pasted on the polyimide film layer, a 25 mm width is cut, and the polyimide film adhered to the Lami-off recycled paper craft tape is pulled. The peel strength was measured. The carrier substrate on which the polyimide film layer was laminated was subjected to peel strength measurement after being left in a vacuum state overnight before measurement for humidity control.

<Synthesis Example 1>
(Synthesis of 1,1′-bicyclohexane-3,3 ′, 4,4′-tetracarboxylic acid-3,3 ′, 4,4′-dianhydride (H-BPDA))

  1,1′-biphenyl-3, obtained by dissolving 150 g of 1,1′-biphenyl-3,3 ′, 4,4′-tetracarboxylic dianhydride in a solution of 593 g of water and 83.3 g of sodium hydroxide , 3 ′, 4,4′-tetracarboxylic acid tetrasodium salt aqueous solution was subjected to nuclear hydrogenation at 10 MPaG and 120 ° C. using a Ru / C catalyst. Subsequently, 429 g of a 49% aqueous sulfuric acid solution was added dropwise to precipitate and filtered to obtain 157 g (yield 81%) of dicyclohexyl-3,3 ′, 4,4′-tetracarboxylic acid.

  Into a 300 ml three-necked flask equipped with a thermometer, a stirrer and a Dimroth condenser, dicyclohexyl-3,3 ′, 4,4′-tetracarboxylic acid (H-BTC) obtained above under nitrogen is obtained. 7 g (0.98 mol) and 90 g of acetic anhydride were added. This was heated with stirring and reacted at reflux temperature (130 ° C. to 140 ° C.) for 3 hours. After the reaction, it was cooled to 10 ° C. and filtered to obtain white crystals. The obtained crystals were washed with toluene and dried with a vacuum dryer to obtain 1,1′-bicyclohexane-3,3 ′, 4,4′-tetracarboxylic acid-3,3 ′, 4. , 4'-dianhydride (H-BPDA) containing composition 23.5g (yield 78%) was obtained.

<Synthesis Example 2>
(Preparation of polyamic acid resin solution 1)
1,1′-bicyclohexane-3,3 ′, 4,4′-tetracarboxylic acid-3,3 ′, 4,4′-dianhydride (H-BPDA) 60.0 g obtained in Synthesis Example 1 (196 mmol) was added to N, N-dimethylacetamide (127.5 g), and the mixture was stirred at room temperature under a nitrogen stream. A solution prepared by dissolving 39.6 g (198 mmol) of 4,4′-diaminodiphenyl ether (ODA) (manufactured by Tokyo Chemical Industry Co., Ltd.) in 171.3 g of N, N-dimethylacetamide was added and stirred at 80 ° C. for 6 hours. A target polyamic acid resin solution 1 was obtained.

<Synthesis Example 3>
(Preparation of polyimide resin solution 1)
In a 4-neck flask equipped with a dry nitrogen gas inlet tube, a condenser, a Dean-Stark aggregator filled with toluene, and a stirrer, the polyamic acid ester resin solution (50 g) obtained in Synthesis Example 2 and 7.5 g of toluene, triethylamine 0.09g was added and the inside of a three necked flask was made into nitrogen atmosphere. The external temperature was heated to 190 ° C., and water generated during imidization was distilled off azeotropically with toluene. When heating, refluxing, and stirring were continued for 6 hours, generation of water was not observed. Subsequently, the mixture was heated for 7 hours while distilling off toluene and triethylamine to obtain a polyimide resin solution 1.

<Synthesis Example 4>
(Preparation of polyamic acid resin solution 2)
Add 3.65 g (29.4 mmol) of 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride (BPDA) to N, N-dimethylacetamide (59.0 g) and stir at room temperature under a nitrogen stream. did.
To this, 6.01 g (30.0 mmol) of 4,4′-diaminodiphenyl ether (ODA) (manufactured by Wakayama Seika Co., Ltd.) was added, and the mixture was heated and stirred at 80 ° C. for 6 hours to obtain the target polyamic acid resin solution 2.

<Synthesis Example 5>
(Preparation of polyamic acid resin solution 3)
Add 1.66 g (29.7 mmol) of 1,2,4,5-cyclohexanetetracarboxylic dianhydride (trans) (HS-PMDA) (manufactured by Wako Pure Chemical Industries, Ltd.) to N, N-dimethylacetamide (38 g). The mixture was stirred at room temperature under a nitrogen stream. To this, 6.01 g (30.0 mmol) of 4,4′-diaminodiphenyl ether (ODA) (manufactured by Wakayama Seika Co., Ltd.) was added, and the mixture was heated and stirred at 80 ° C. for 6 hours to obtain the desired polyamic acid resin solution 3.

<Synthesis Example 6>
(Preparation of polyamic acid resin solution 4)
2,2-bis (3,4-dicarboxyphenyl) -1,1,1,3,3,3-hexafluoropropane dianhydride (6FDA) (manufactured by Daikin Industries) 21.99 g (49.5 mmol) Was added to N, N-dimethylacetamide (96 g), and the mixture was stirred at room temperature under a nitrogen stream. Thereto was added 10.01 g (50.0 mmol) of 4,4′-diaminodiphenyl ether (ODA) (manufactured by Wakayama Seika Co., Ltd.), and the mixture was heated and stirred at 80 ° C. for 6 hours to obtain the desired polyamic acid resin solution 4.

<Synthesis Example 7>
(Preparation of polyamic acid resin solution 5)
1,1′-bicyclohexane-3,3 ′, 4,4′-tetracarboxylic acid-3,3 ′, 4,4′-dianhydride (H-BPDA) 84.6 g (276 mmol) and 2,2 -Bis (3,4-dicarboxyphenyl) -1,1,1,3,3,3-hexafluoropropane dianhydride (6FDA) (manufactured by Daikin Industries) 9.24 g (20.8 mmol) , N-dimethylacetamide (462 g) and stirred at room temperature under a nitrogen stream. 60.1 g (300 mmol) of 4,4′-diaminodiphenyl ether (ODA) (manufactured by Wakayama Seika Co., Ltd.) was added thereto, and the mixture was heated and stirred at 80 ° C. for 6 hours to obtain the target polyamic acid resin solution 5.

<Synthesis Example 8>
(Preparation of polyimide resin solution 2)
1,1′-bicyclohexane-3,3 ′, 4,4′-tetracarboxylic acid-into a four-necked flask equipped with a dry nitrogen gas introduction tube, a condenser, a Dean-Stark agglomerator filled with toluene, and a stirrer 30.34 g (99 mmol) of 3,3 ′, 4,4′-dianhydride (H-BPDA) was added to N, N-dimethylacetamide (154 g) and stirred at room temperature under a nitrogen stream.
21.0 g (100 mmol) of 4,4′-diamino-2,2′-dimethylbiphenyl (m-TB) (manufactured by Wakayama Seika Co., Ltd.) was added thereto, and the mixture was heated and stirred at 80 ° C. for 6 hours. Thereafter, the external temperature was heated to 190 ° C., and water generated along with imidization was distilled off azeotropically with toluene.
When heating, refluxing, and stirring were continued for 6 hours, generation of water was not observed. Subsequently, the mixture was heated for 7 hours while distilling off toluene to obtain the target polyimide resin solution 2.

<Synthesis Example 9>
(Preparation of polyimide resin solution 3)
2,2-bis (3,4-dicarboxyphenyl) -1,1,1,3 was added to a four-necked flask equipped with a dry nitrogen gas inlet tube, a condenser, a Dean-Stark aggregator filled with toluene, and a stirrer. , 3,3-hexafluoropropane dianhydride (6FDA) (manufactured by Daikin Industries, Ltd.) 25.59 g (57.6 mmol) was added to N, N-dimethylacetamide (134 g), and the mixture was stirred at room temperature under a nitrogen stream.
To the solution, 19.2 g (60 mmol) of 4,4′-diamino-2,2′-bis (trifluoromethyl) biphenyl (TFMB) (manufactured by Daikin Industries) was added, and the mixture was heated and stirred at 80 ° C. for 6 hours. Thereafter, the external temperature was heated to 190 ° C., and water generated along with imidization was distilled off azeotropically with toluene. When heating, refluxing, and stirring were continued for 6 hours, generation of water was not observed. Subsequently, the mixture was heated for 7 hours while distilling off toluene to obtain the target polyimide resin solution 3.

<Example 1>
A blue glass plate (125 × 125 mm, 18 mm thickness) was used as the carrier substrate.
2.4 g of a silane coupling agent (hexyltrimethoxysilane) was mixed with 27.2 g of ethanol, dropped into acetic acid water adjusted to pH 4, and then stirred at room temperature for 2 hours. A soda-lime glass washed with an alkaline surfactant and distilled water was immersed in this solution for 3 minutes. The glass was taken out, rinsed with distilled water, and then dried by heating with a hot air dryer at 60 ° C. for 1 hour to provide a silane coupling layer.

  The polyamic acid resin solution 1 obtained in Synthesis Example 2 was cast to a thickness of 254 μm on the glass plate provided with the silane coupling layer as described above, using a film applicator, and 30 minutes at 80 ° C. under reduced pressure. Dried. Then, it was dried at 80 ° C. for 30 minutes under vacuum, further heated to 200 ° C. at 2 ° C./min under nitrogen, and dried at 200 ° C. for 1 hour. Further, a polyimide film layer was produced on a glass plate having a silane coupling layer by heating in an inert oven under nitrogen at 250 ° C. for 30 minutes and further at 300 ° C. for 30 minutes. About the obtained laminated body, peel strength was measured according to the method as described above. The evaluation results are shown in Table 1.

<Example 2>
Silane coupling agent (polydimethylsiloxane: Silicone L-25 (Fuji Rika Kogyo Co., Ltd.) (4.0 g) was dropped into distilled water to prepare a silane coupling solution.Alkaline surfactant and distillation as in Example 1. Blue plate glass washed with water was immersed in this solution for 3 minutes, and the glass was taken out, rinsed with distilled water, dried by heating with a hot air dryer at 60 ° C. for 1 hour to provide a silane coupling layer in a glassy state.
A polyimide film layer was provided in the same manner as in Example 1 except that the polyamic acid resin solution 1 obtained in Synthesis Example 2 was used. About the obtained laminated body, peel strength was measured according to the method as described above. The evaluation results are shown in Table 1.

<Example 3>
A laminate was obtained in the same manner as in Example 1 except that the polyamic acid resin solution 1 obtained in Synthesis Example 2 was changed to the polyimide resin solution 1 obtained in Synthesis Example 3. About the obtained laminated body, peel strength was measured according to the method as described above. The evaluation results are shown in Table 1.

<Example 4>
A laminate was obtained in the same manner as in Example 2 except that the polyamic acid resin solution 1 obtained in Synthesis Example 2 was changed to the polyimide resin solution 1 obtained in Synthesis Example 3. About the obtained laminated body, peel strength was measured according to the method as described above. The evaluation results are shown in Table 1.

<Example 5>
The polyamic acid resin solution 2 obtained in Synthesis Example 4 was cast at a thickness of 254 μm on a glass plate provided with a silane coupling layer by the method of Example 1 using a film applicator.
Subsequently, using an inert oven, the glass was dried at 80 ° C. for 10 minutes in a nitrogen atmosphere, then heated to 300 ° C. at 2 ° C./min, and heated at 300 ° C. for 30 minutes to provide a silane coupling layer. A polyimide film layer was created on the plate.
About the obtained laminated body, peel strength was measured according to the method as described above. The evaluation results are shown in Table 1.

<Example 6>
It implemented like Example 5 except having changed the glass plate which provided the silane coupling layer into the glass plate which provided the silane coupling layer by the method of Example 2. FIG. About the obtained laminated body, peel strength was measured according to the method as described above. The evaluation results are shown in Table 1.

<Example 7>
A laminate was obtained in the same manner as in Example 5 except that the polyamic acid resin solution 2 obtained in Synthesis Example 4 was changed to the polyamic acid resin solution 3 obtained in Synthesis Example 5. About the obtained laminated body, peel strength was measured according to the method as described above. The evaluation results are shown in Table 1.

<Example 8>
A laminate was obtained in the same manner as in Example 6 except that the polyamic acid resin solution 2 obtained in Synthesis Example 4 was changed to the reamic acid resin solution 3 obtained in Synthesis Example 5. About the obtained laminated body, peel strength was measured according to the method as described above. The evaluation results are shown in Table 1.

<Example 9>
A laminate was obtained in the same manner as in Example 5 except that the polyamic acid resin solution 2 obtained in Synthesis Example 4 was changed to the reamic acid resin solution 4 obtained in Synthesis Example 6. About the obtained laminated body, peel strength was measured according to the method as described above. The evaluation results are shown in Table 1.

<Example 10>
A laminate was obtained in the same manner as in Example 6 except that the polyamic acid resin solution 2 obtained in Synthesis Example 4 was changed to the reamic acid resin solution 4 obtained in Synthesis Example 6. About the obtained laminated body, peel strength was measured according to the method as described above. The evaluation results are shown in Table 1.

<Example 11>
A laminate was obtained in the same manner as in Example 5 except that the polyamic acid resin solution 2 obtained in Synthesis Example 4 was changed to the reamic acid resin solution 5 obtained in Synthesis Example 7. About the obtained laminated body, peel strength was measured according to the method as described above. The evaluation results are shown in Table 1.

<Example 12>
A laminate was obtained in the same manner as in Example 6 except that the polyamic acid resin solution 2 obtained in Synthesis Example 4 was changed to the reamic acid resin solution 5 obtained in Synthesis Example 7. About the obtained laminated body, peel strength was measured according to the method as described above. The evaluation results are shown in Table 1.

<Example 13>
A laminate was obtained in the same manner as in Example 5 except that the polyamic acid resin solution 2 obtained in Synthesis Example 4 was changed to the polyimide resin solution 2 obtained in Synthesis Example 8. About the obtained laminated body, peel strength was measured according to the method as described above.
In the peel strength measurement, no peeling from the glass substrate was observed before the film was cut. However, when the film was cut, it was easily peeled off, and it was difficult to specify the value by measuring the peel strength, so it was estimated that the value range was larger than 0 and smaller than 2 of the measurement limit value. The evaluation results are shown in Table 1.

<Example 14>
A laminate was obtained in the same manner as in Example 6 except that the polyamic acid resin solution 2 obtained in Synthesis Example 4 was changed to the polyimide resin solution 2 obtained in Synthesis Example 8. About the obtained laminated body, peel strength was measured according to the method as described above.
In the peel strength measurement, no peeling from the glass substrate was observed before the film was cut. However, when the film was cut, it was easily peeled off, and it was difficult to specify the value by measuring the peel strength, so it was estimated that the value range was larger than 0 and smaller than 2 of the measurement limit value. The evaluation results are shown in Table 1.

<Example 15>
A laminate was obtained in the same manner as in Example 5 except that the polyamic acid resin solution 2 obtained in Synthesis Example 4 was changed to the polyimide resin solution 3 obtained in Synthesis Example 9. About the obtained laminated body, peel strength was measured according to the method as described above.
In the peel strength measurement, no peeling from the glass substrate was observed before the film was cut. However, when the film was cut, it was easily peeled off, and it was difficult to specify the value by measuring the peel strength, so it was estimated that the value range was larger than 0 and smaller than 2 of the measurement limit value. The evaluation results are shown in Table 1.

<Example 16>
A laminate was obtained in the same manner as in Example 6 except that the polyamic acid resin solution 2 obtained in Synthesis Example 4 was changed to the polyimide resin solution 3 obtained in Synthesis Example 9. About the obtained laminated body, peel strength was measured according to the method as described above.
In the peel strength measurement, no peeling from the glass substrate was observed before the film was cut. However, when the film was cut, it was easily peeled off, and it was difficult to specify the value by measuring the peel strength, so it was estimated that the value range was larger than 0 and smaller than 2 of the measurement limit value. The evaluation results are shown in Table 1.

<Comparative Example 1>
The polyamic acid resin solution 1 obtained in Synthesis Example 2 is cast at a thickness of 254 μm on a blue plate glass washed with an alkaline surfactant and distilled water using a film applicator, and dried at 80 ° C. for 30 minutes under reduced pressure. did. Thereafter, it was dried at 80 ° C. for 30 minutes under vacuum, further heated to 200 ° C. at 2 ° C./min under nitrogen, and dried at 200 ° C. for 1 hour. Furthermore, it was heated at 250 ° C. for 30 minutes under nitrogen in an inert oven and further at 300 ° C. for 30 minutes to provide a polyimide film layer on a glass plate to obtain a laminate. About the obtained laminated body, peel strength was measured according to the method as described above. The evaluation results are shown in Table 1.

<Comparative example 2>
A laminate was obtained in the same manner as in Example 1 except that the silane coupling agent (hexyltrimethoxysilane) was changed to 3-aminopropyltrimethoxysilane. About the obtained laminated body, peel strength was measured according to the method as described above. However, since the adhesion between the glass substrate and the polyimide film was strong, the polyimide film layer was destroyed before the polyimide film was peeled from the glass substrate, and measurement was impossible. The evaluation results are shown in Table 1.

<Comparative Example 3>
A laminate was obtained in the same manner as in Example 1 except that 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane was used as the silane coupling agent (hexyltrimethoxysilane). About the obtained laminated body, peel strength was measured according to the method as described above. However, since the adhesion between the glass substrate and the polyimide film layer was strong, the polyimide film layer was broken before the polyimide film layer was peeled from the glass substrate, and measurement was impossible. The evaluation results are shown in Table 1.

<Comparative example 4>
A laminate was obtained in the same manner as in Comparative Example 1 except that the polyamic acid resin solution 1 obtained in Synthesis Example 2 was changed to the polyimide resin solution 1 obtained in Synthesis 3. About the obtained laminated body, peel strength was measured according to the method as described above. The evaluation results are shown in Table 1.

<Comparative Example 5>
A laminate was obtained in the same manner as in Comparative Example 2 except that the polyamic acid resin solution 1 obtained in Synthesis Example 2 was changed to the polyimide resin solution 1 obtained in Synthesis 3. About the obtained laminated body, peel strength was measured according to the method as described above. However, since the adhesion between the glass substrate and the polyimide film layer was strong, the polyimide film layer was broken before the polyimide film layer was peeled from the glass substrate, and measurement was impossible. The evaluation results are shown in Table 1.

<Comparative Example 6>
A laminate was obtained in the same manner as in Comparative Example 3 except that the polyamic acid resin solution 1 obtained in Synthesis Example 2 was changed to the polyimide resin solution 1 obtained in Synthesis 3. About the obtained laminated body, peel strength was measured according to the method as described above. However, since the adhesion between the glass substrate and the polyimide film layer is strong, the polyimide film was destroyed before the polyimide film was peeled from the glass substrate, and measurement was impossible. The evaluation results are shown in Table 1.

  Examples 1-16 show the favorable peelability with respect to Comparative Examples 1-6, and obtain the laminated body for devices which can perform the peeling of the polyimide film layer from a carrier substrate easily and efficiently. I was able to.

Claims (7)

A method for producing a laminate including a carrier substrate, a silane coupling layer and a polyimide film layer,
Providing a silane coupling layer on the carrier substrate surface;
A step of applying a polyamic acid resin solution and / or a polyimide resin solution on the silane coupling layer and providing a polyimide film layer by drying;
The step of providing the silane coupling layer uses a silane coupling agent that does not contain an epoxy group and an amino group, and the polyimide film layer includes a structure represented by the following general formula (8).
A manufacturing method of a layered product.

[In the general formula (8), R ³ represents a tetravalent organic group,
R ⁴ represents a divalent organic group,
n represents an integer of 1 or more, and when n is 2 or more, a plurality of R ³ and R ⁴ present in one molecule of the structure represented by the general formula (8) may be the same or different. . ] The method for producing a laminate according to claim 1, wherein the step of providing the silane coupling layer uses at least one silane coupling agent selected from the following general formulas (1) to (3).

(In general formula (1),
A ^{1 to} A ⁴ each independently represents an organic group that does not contain an epoxy group and an amino group,
At least one of A ^{1 to} A ⁴ represents an alkoxy group which may have a substituent, an acyloxy group which may have a substituent, or a halogen atom. )

(In General Formula (2), A ^{5 to} A ⁷ each independently have an alkyl group which may have a substituent, an acyl group which may have a substituent, or a substituent. The alkyl group, the acyl group, and the substituent that the aromatic group may have does not include an epoxy group and an amino group, and Y ¹ does not include an epoxy group and an amino group. represents a group, m ¹ represents an integer of 2 or more, m ³ is Y ¹ and a ⁷ there are a plurality of the silane coupling agent in one molecule represented by 0 or 1. general formula (2) in the same It may or may not be.)

(In General Formula (3), A ^{8 to} A ¹³ each independently have an alkyl group which may have a substituent, an alkoxy group which may have a substituent, or a substituent. An acyloxy group which may be present, and the substituent which the alkyl group, alkoxy group and acyloxy group may have does not include an epoxy group and an amino group,
X ¹ represents a —NH— group or a group represented by the following general formula (4).

(In the general formula (4), R ¹ and R ² each independently have a substituent indicates also alkylene group, the substituent which may be the alkylene groups have epoxy group and amino No group is included, and m ² represents an integer of 1 or more.) The method for producing a laminate according to claim 1, wherein R ^{4 in the} general formula (8) is represented by the following general formula (10).

(In General Formula (10), Ring A ²⁰ and Ring A ²¹ are each independently an alicyclic hydrocarbon group which may have a substituent, or an aromatic group which may have a substituent. Indicate
p and q each independently represent an integer of 0 or more and 10 or less. However, neither p nor q is 0.
X ⁴ is a direct bond, an oxygen atom, a sulfur atom, an alkylene group which may have a substituent, a sulfonyl group, a sulfinyl group, a sulfide group, a carbonyl group, an aromatic group which may have a substituent,- NH-C (= O) - group or an -NH- group, or -O-CzH ₂ z-O- group, z is an integer of 1 to 5.
Y ¹⁰ and Y ¹¹ each independently represent a direct bond, an oxygen atom, a sulfur atom, an optionally substituted alkylene group, a sulfonyl group, a sulfinyl group, a sulfide group, or a carbonyl group. When p and / or q is 2 or more, the plurality of Y ¹⁰ , Y ¹¹ , ring A ²⁰ and ring A ²¹ may be different from each other. ) The said general formula (8) is shown by the following general formula (9), The manufacturing method of the laminated body of any one of Claims 1-3 characterized by the above-mentioned.

[In general formula (9), R ⁵ represents a divalent organic group,
a represents an integer of 1 or more, and when a is 2 or more, a plurality of R ⁵ present in one molecule of the structure represented by the general formula (9) may be the same or different. ] A laminate having a silane coupling layer between a carrier substrate and a polyimide film layer, wherein the silane coupling layer is derived from a silane coupling agent represented by the following general formulas (1) to (3) A laminate comprising a group, wherein the polyimide film layer has a structure represented by the following general formula (8).

(In general formula (1),
A ^{1 to} A ⁴ each independently represents an organic group that does not contain an epoxy group and an amino group,
At least one of A ^{1 to} A ⁴ represents an alkoxy group which may have a substituent, an acyloxy group which may have a substituent, or a halogen atom. )

(In General Formula (2), A ^{5 to} A ⁷ each independently have an alkyl group which may have a substituent, an acyl group which may have a substituent, or a substituent. The alkyl group, the acyl group and the substituent that the aromatic group may have does not include an epoxy group and an amino group, and Y ¹ does not include an epoxy group and an amino group, Represents an organic group, m ¹ represents an integer of 2 or more, and m ³ represents 0 or 1. A plurality of Y ¹ and A ⁷ present in one molecule of the silane coupling agent represented by the general formula (2) are the same. Or different.)

(In General Formula (3), A ^{8 to} A ¹³ each independently have an alkyl group which may have a substituent, an alkoxy group which may have a substituent, or a substituent. An acyloxy group which may be present, and the substituent which the alkyl group, alkoxy group and acyloxy group may have does not include an epoxy group and an amino group,
X ¹ represents a —NH— group or a group represented by the following general formula (4).

(In the general formula (4), R ¹ and R ² each independently have a substituent indicates also alkylene group, the substituent which may be the alkylene groups have epoxy group and amino No group is included, and m ² represents an integer of 1 or more.)

[In the general formula (8), R ³ represents a tetravalent organic group,
R ⁴ represents a divalent organic group,
n represents an integer of 1 or more, and when n is 2 or more, a plurality of R ³ and R ⁴ present in one molecule of the structure represented by the general formula (8) may be the same or different. . ]   A device laminate in which a device is formed on the laminate according to claim 5.   A device film obtained by peeling a carrier substrate from the device laminate according to claim 6.