JP2012233083A - Device manufacturing method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for manufacturing a device in which a circuit is formed on a resin film more inexpensively and with higher producibility than before.SOLUTION: This method for manufacturing a device includes: a step of applying a liquid polyimide resin composition onto a carrier substrate and drying the resultant coating film to form a solid polyimide resin film on the carrier substrate; a step of forming a circuit on the polyimide resin film; and a step of peeling the polyimide resin film in which a circuit is formed from the carrier substrate, in which the liquid polyimide resin composition contains a polyimide resin containing a repeating unit represented by Formula (1) (where Rrepresents a divalent organic group), and a solvent.

Description

  The present invention relates to a device manufacturing method, and more particularly to a device manufacturing method including a polyimide resin film having a specific skeleton.

  Currently, plastic film (resin film) substrates are attracting attention as substitutes for glass substrates that are generally used in various devices. In particular, a highly transparent plastic film substrate has attracted attention as a substrate for flexible devices such as displays, organic EL, or photoelectric conversion elements.

  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.

  When manufacturing a device in which a circuit is formed on a plastic film substrate, it is possible to form a plastic film on a carrier substrate, form a circuit on the plastic film, and then remove the plastic film on which the circuit is formed. This is preferable in that the cost can be reduced by simplification. For example, Patent Document 1 discloses a process of forming a solid resin film by coating and forming a polyimide precursor resin composition mainly composed of a liquid polyamic acid on a carrier substrate, and forming a circuit on the resin film. A method of obtaining a flexible device by a step of performing and a step of peeling a resin film having a circuit formed on a surface thereof from a carrier substrate.

  Patent Document 2 discloses a step of forming a polyimide film substrate on a support surface-treated with a silicon mold release agent, a step of providing a photoelectric conversion element on the substrate, and a substrate from the support. And a method of producing an amorphous silicon solar cell by the separating step.

JP 2010-202729 A Japanese Patent Laid-Open No. 2-49475

  A surface-treated substrate, a substrate coated with a release agent, a silicon substrate, or the like requires a relatively high cost to prepare. In order to reduce the manufacturing cost of the device, it is preferable to use an inexpensive carrier substrate such as glass.

  However, according to the study by the inventors of the present application, it has been found that, in the method described in Patent Document 1, for example, when a glass substrate is used, the resin film is firmly bonded to the carrier substrate. If a stronger force is applied to peel off the strongly adhered resin film, the resin film may be deteriorated such as warpage. Further, when the resin film is peeled off with a strong force, the circuit on the resin film may be damaged, and the production efficiency may be reduced. Further, as another method, a method of immersing the resin film in water and a method of irradiating the resin film with a laser are conceivable. However, such a method not only causes the resin film to absorb water or deteriorates, but also the resin film. Damage to the circuitry on the membrane can occur.

  Further, according to the study by the present inventors, it has been found that it is not easy to peel off the produced solar cell from the support even in the method described in Patent Document 2. Moreover, the polyimide resin described in Patent Document 2 has a problem in terms of transparency, and may be a problem when transparency is required.

  An object of this invention is to manufacture the device by which a circuit is formed on a resin film more inexpensively and with high manufacturing efficiency.

  In view of the above circumstances, the present inventors have intensively studied a method for easily and efficiently peeling a device in which a circuit is formed on a resin film from a carrier substrate. As a result, the object of the present invention is achieved by forming a polyimide resin film by applying a composition containing a polyimide resin having a specific structure on a carrier substrate, and forming a circuit on the resin film. The present invention has been completed.

（式（１）中、Ｒ^１は２価の有機基を示す。）
［２］Ｒ^１が下記式（２）で表される有機基であることを特徴とする、［１］に記載のデバイス製造方法。

（式（２）中、環Ａ及び環Ｂは各々独立して、置換基を有していてもよい芳香族環又は置換基を有していてもよい脂肪族環を示し、ｐ、ｑは各々独立して、０〜１０の整数を示す。Ｘは直接結合、酸素原子、硫黄原子、置換基を有していてもよいアルキレン基、スルホニル基、スルフィニル基、スルフィド基、カルボニル基、芳香族基、−ＮＨ−、又は−Ｏ−Ｃ_ｎＨ_２ｎ−Ｏ−（ｎは１〜５の整数）を示す。Ｙ^１及びＹ^２は各々独立して、直接結合、酸素原子、硫黄原子、置換基を有していてもよいアルキレン基、スルホニル基、スルフィニル基、スルフィド基、又はカルボニル基を示す。ｐ又はｑが２以上である場合、複数のＹ^１又はＹ^２は互いに異なっていてもよい。）
［３］前記ポリイミド樹脂膜は、ＪＩＳ Ｋ ７３６１−１による４００ｎｍにおける全光線透過率が７０％以上であることを特徴とする、［１］又は［２］に記載のデバイス製造方法。 The present invention relates to the following items.
[1] A step of forming a solid polyimide resin film on the carrier substrate by applying and drying the liquid polyimide resin composition on the carrier substrate;
Forming a circuit on the polyimide resin film;
Peeling the polyimide resin film on which the circuit is formed from the carrier substrate;
A device manufacturing method comprising:
The said liquid polyimide resin composition contains the polyimide resin containing the repeating unit represented by following formula (1), and a solvent, The device manufacturing method characterized by the above-mentioned.

(In formula (1), R ¹ represents a divalent organic group.)
[2] The device manufacturing method according to [1], wherein R ¹ is an organic group represented by the following formula (2).

(In Formula (2), each of ring A and ring B independently represents an aromatic ring which may have a substituent or an aliphatic ring which may have a substituent, and p and q are Each independently represents an integer of 0 to 10. X represents 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 an aromatic group. A group, —NH—, or —O—C _n H _2n —O— (n is an integer of 1 to 5.) Y ¹ and Y ² are each independently a direct bond, an oxygen atom, a sulfur atom, or a substituent. Represents an alkylene group, a sulfonyl group, a sulfinyl group, a sulfide group, or a carbonyl group, which may have a group, and when p or q is 2 or more, a plurality of Y ¹ or Y ² may be different from each other. .)
[3] The device manufacturing method according to [1] or [2], wherein the polyimide resin film has a total light transmittance at 400 nm of 70% or more according to JIS K 7361-1.

  A device in which a circuit is formed on a resin film can be manufactured at lower cost and with higher manufacturing efficiency.

The figure explaining the device manufacturing method which concerns on an example of embodiment of this invention.

  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.

  The manufacturing method of the flexible device in the present embodiment includes a step of forming a solid polyimide resin film on the carrier substrate by applying the liquid polyimide resin composition on the carrier substrate and drying, and the polyimide resin film. A step of forming a circuit thereon, and a step of peeling the polyimide resin film on which the circuit is formed from the carrier substrate. This liquid polyimide resin composition contains a polyimide resin containing a repeating unit represented by the following formula (1) and a solvent.

式（１）において、Ｒ^１は２価の有機基を示す。

In the formula (1), R ¹ represents a divalent organic group.

  According to this method, there is no need to transfer a separately manufactured circuit to the resin film, and the circuit can be formed directly on the polyimide resin film. According to this method, the polyimide resin film on which the circuit is formed can be easily peeled off from the carrier substrate. This can reduce damage to the polyimide resin film and the circuit when the device is peeled off, so that the durability of the device tends to be improved. Furthermore, by applying a liquid polyimide resin composition having a low polyamic acid resin content and forming a polyimide resin film, it is possible to reduce the generation of water accompanying dehydration and ring closure. The occurrence of film defects can be suppressed. Further, in the subsequent step of forming a circuit on the polyimide resin film, generation of outgas from the polyimide resin film can be reduced. Furthermore, since the polyimide resin film can be obtained simply by removing the solvent from the liquid polyimide resin composition, the processing conditions in the process of forming the resin film such as the heating time and the heating temperature can be moderated. In the process of manufacturing, the load on the polyimide resin film can be reduced.

<1. Liquid polyimide resin composition>
Below, the liquid polyimide resin composition used in this embodiment is demonstrated. The liquid polyimide resin composition which concerns on this embodiment contains the polyimide resin (polyimide resin which concerns on this embodiment) which has a structure represented by General formula (1), and a solvent (solvent which concerns on this embodiment). Hereinafter, the polyimide resin according to the present embodiment and the solvent according to the present embodiment will be described.

<1.1 Polyimide resin>
The polyimide resin according to the present embodiment includes a repeating unit represented by the following general formula (1).

式（１）において、Ｒ^１は２価の有機基を示す。なお、本実施形態に係るポリイミド樹脂は一般式（１）で表される繰り返し単位を複数含むため、複数の２価の有機基Ｒ^１が含まれる。ここで、複数の２価の有機基Ｒ^１は全て同じ構造を有してもよいし、異なる構造を有してもよい。

In the formula (1), R ¹ represents a divalent organic group. Incidentally, the polyimide resin according to the present embodiment is the general formula (1) for containing a plurality of repeating units represented by include organic groups R ¹ of a plurality of divalent. Here, the plurality of divalent organic groups R ¹ may all have the same structure or different structures.

  Thus, the polyimide resin of the present embodiment is reduced in coloring compared to a polyimide resin composed of an aromatic ring such as biphenyl or a tetracarboxylic acid residue having a monocyclic aliphatic ring as a skeleton, In addition, the effect of improving the solubility can be obtained. Moreover, the polyimide resin according to the present embodiment has relatively high solubility, and the solution concentration can be freely adjusted. Furthermore, the polyimide resin according to this embodiment is relatively excellent in heat resistance and transparency.

R ¹ is not particularly limited as long as it is a divalent organic group, but a resin film having high transparency and heat resistance can be obtained when it is a divalent organic group represented by the general formula (2). In addition, it is preferable in that coloring due to deterioration of the resin film with time can be reduced and solubility in an organic solvent is improved. In order to obtain these effects, the ratio of the repeating unit represented by the general formula (1) to all the repeating units contained in the polyimide resin is preferably 50% or more, more preferably 70%. Or more, more preferably 90% or more, and most preferably 95% or more.

In formula (2), ring A and ring B each independently represent an aromatic ring which may have a substituent or an aliphatic ring which may have a substituent. Ring A and ring B may be monocyclic groups or condensed ring groups. In addition, when p or q is 2 or more, R ¹ has a plurality of rings A or B, but these rings A or B may be rings having the same structure or different from each other. It may be a ring of structure.

  The aromatic ring is not particularly limited, and examples thereof include an aromatic hydrocarbon ring and an aromatic heterocyclic ring. Examples of the aromatic hydrocarbon ring include benzene ring, naphthalene ring, azulene ring, biphenyl ring, acenaphthylene ring, fluorene ring, phenanthrene ring, anthracene ring, fluoranthene ring, triphenyl ring, terphenyl ring, pyrene ring, chrysene ring. , Naphthacene ring, perylene ring, and pentacene ring, and those having 6 to 30 carbon atoms. Carbon number becomes like this. Preferably it is 6-25, More preferably, it is 6-20. Examples of the aromatic heterocyclic ring include those having 2 to 30 carbon atoms such as a pyrrole ring, a furan ring, a thiophene ring, a pyridine ring, a quinoline ring, and an isoquinoline ring. Carbon number becomes like this. Preferably it is 2-25, More preferably, it is 2-20. Among these, a benzene ring, a biphenylene ring, and a terphenyl ring are preferable.

  The aliphatic ring is not particularly limited, but includes a cyclobutane ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, norbornane ring, norbornene ring, hydrindane ring, decahydronaphthalene ring, adamantane ring, etc. The thing of carbon numbers 3-30 is mentioned. Preferably carbon number is 3-25. Among these, a cyclohexane ring, a cyclopentane ring, and a norbornane ring are preferable.

Regarding the aromatic ring or aliphatic ring that is ring A or ring B, the position of bonding to Y ¹ , Y ² , or X is not particularly limited.

  Examples of the substituent that the aromatic ring or the aliphatic ring 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.

  In the formula (2), 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 (2), X 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, and an aromatic which may have a substituent. Represents a group, —NH—, or —O—C _n H _2n —O—. However, n shows the integer of 1-5. Among these, a direct bond, an oxygen atom, an alkylene group that may have a substituent, a sulfinyl group, or a sulfonyl group is preferable, an oxygen atom, an alkylene group that may have a substituent, or A sulfinyl group is particularly preferred.

  Although there is no special restriction | limiting as an alkylene group, It is preferable that it is a C1-C20 alkylene group, and it is more preferable that it is a C1-C10 alkylene group. 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 is not particularly limited, and examples thereof include an aromatic hydrocarbon group and an aromatic heterocyclic group. Examples of the aromatic hydrocarbon group include those having 6 to 30 carbon atoms such as a phenylene group, a biphenylene group, a naphthylene group, a phenanthrene group, a triphenylene group, a terphenylene group, a pyrenylene group, and a fluorene group. Examples of the aromatic heterocyclic group include those having 2 to 30 carbon atoms such as a pyridylene group and a quinolylene group. Among these, a phenylene group, a naphthylene group, and a pyridylene group are preferable.

  Examples of the substituent that the alkylene group or aromatic group 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 ¹ and Y ² 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. Among these, a direct bond or an oxygen atom is preferable. When p or q is 2 or more, R ¹ includes a plurality of Y ¹ and Y ^2, and the plurality of Y ¹ and Y ² 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 can be used.

It is preferable that the ring A and the ring B have the same structure, and it is also preferable that Y ¹ and Y ² have the same structure.

More preferable examples of R ¹ include those represented by the following general formula (3) or (4).

Equation (3) corresponds to the case where p = 2 and q = 2 in Equation (2). In Formula (3), Ring A, Ring B, Ring C, and Ring D represent the same structure as Ring A and Ring B in Formula (2). Y ¹ , Y ² , Y ³ , and Y ⁴ represent the same structure as Y ¹ and Y ² in Formula (2). Similarly to formula (2), ring A, ring B, ring C and ring D may be different from each other, and Y ¹ , Y ² , Y ³ and Y ⁴ may be different from each other. It is also preferable that the ring A and the ring B have the same structure, and it is also preferable that the ring C and the ring D have the same structure. It is also preferable that Y ¹ and Y ² have the same structure, and it is also preferable that Y ³ and Y ⁴ have the same structure.

In formula (3), ring A, ring B, ring C and ring D are preferably aromatic rings which may have a substituent, and are phenylene groups which may be substituted with a halogen atom. Is more preferable, and a phenylene group is particularly preferable. Y ¹ and Y ² are preferably a direct bond, an oxygen atom, or a sulfur atom. Preferable examples of Y ³ and Y ⁴ include direct bonding.

Equation (4) corresponds to the case where p = 1 and q = 1 in Equation (2). In Formula (4), Ring A and Ring B represent the same structure as Ring A and Ring B in Formula (2). Y ¹ and Y ² represent the same structure as Y ¹ and Y ² in Formula (2). Here, it is also preferable that the ring A and the ring B have the same structure, and it is also preferable that Y ¹ and Y ² have the same structure.

In the formula (4), the ring A and the ring B are preferably an aromatic ring which may have a substituent or an aliphatic ring which may have a substituent, and is substituted with a halogen atom. More preferred is a phenylene group, and particularly preferred is a phenylene group. Preferred examples of ^{Y 1} and ^{Y 2} is a direct bond.

Specific examples of R ¹ include structural units of diamine compounds shown below. That is, a divalent substituent obtained by removing two primary amino groups from the diamine compound shown below can be used as R ¹ . Specific examples of such diamine compounds include 1,4-phenylenediamine, 1,2-phenylenediamine, 1,3-phenylenediamine, 4,4′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, 1, 4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 2,2-bis (4- (4-aminophenoxy) phenyl) propane, 2,2-bis (4- (4-aminophenoxy) phenyl) hexafluoropropane, bis (4- (4-aminophenoxy) phenyl) sulfone, bis (4- (3-aminophenoxy) phenyl) sulfone, 1,3-bis (4-aminophenoxy) ) Neopentane, 4,4'-diamino-3,3'-dimethylbiphenyl, 4,4'-diamino-3,3'-dimethyl Rubiphenyl, 4,4′-diamino-2,2′-dimethylbiphenyl, 4,4′-diamino-2,2′-bis (trifluoromethyl) biphenyl, 4,4′-bis (4-aminophenoxy) Biphenyl, 4,4′-diamino-3,3′-dihydroxybiphenyl, bis (4-amino-3-carboxyphenyl) methane, 4,4′-diaminodiphenylsulfone, bis (4- (4-aminophenoxy) phenyl ) Sulfone, 4,4'-diaminodiphenyl sulfide, N- (4-aminophenoxy) -4-aminobenzamine, 1,4-diaminocyclohexane, 4,4'-methylenebis (cyclohexylamine), 4,4'- And methylene bis (2-methylcyclohexylamine). Among these, 4,4′-diaminodiphenyl ether, 2,2-bis (4- (4-aminophenoxy) phenyl) propane, 2,2-bis (4- (4-aminophenoxy) phenyl) hexafluoropropane, bis Having a divalent substituent obtained by removing an amino group from (4- (4-aminophenoxy) phenyl) sulfone or 4,4′-methylenebis (cyclohexylamine) as R ¹ is transparent, heat resistant Is preferable in that the properties and the mechanical strength can be achieved at the same time.

<1.2 Solvent>
There is no limitation in particular in the solvent which concerns on this embodiment, ie, the solvent which dissolves the polyimide resin which concerns on this embodiment. 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; Among these, N, N-dimethylformamide, N, N-dimethylacetamide, and N-methyl-2-pyrrolidone are particularly preferable. The solvent according to this embodiment may be composed of one kind of substance or a mixture of two or more kinds of substances.

<1.3 Composition of liquid polyimide resin composition>
The concentration of the polyimide resin in the liquid polyimide resin composition according to this embodiment is not particularly limited, but is usually 1% by weight or more, preferably 5% by weight or more, and usually 80% by weight or less, preferably Is 50% by weight or less. By adjusting the concentration of the polyimide resin in the composition within this range, good coatability can be achieved.

Although there is no special restriction | limiting in the viscosity of the liquid polyimide resin composition which concerns on this embodiment, Usually, it is 10 mPa * s or more, Preferably it is 1.0 * 10 < ² > mPa * s or more, On the other hand, usually 5.0 *. It is 10 ⁴ mPa · s or less, preferably 2.0 × 10 ⁴ mPa · s or less. By adjusting the viscosity of the liquid polyimide resin composition within the above range, good coatability can be achieved. In this specification, the viscosity 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 liquid polyimide resin composition according to this embodiment may contain a polyamic acid resin or a polyamic acid ester resin described later. By adding a polyamic acid resin or a polyamic acid ester resin, when forming a film by applying a liquid polyimide resin composition to the coated body, the adhesion between the film and the coated body can be controlled. it can. For example, by increasing the ratio of the polyamic acid resin or the polyamic acid ester resin, the adhesion between the formed film and the coated body can be improved.

  Thus, by adjusting the material composition ratio in the liquid polyimide resin composition, the adhesive strength of the polyimide resin film can be controlled in consideration of the material of the carrier substrate. Therefore, by using the liquid polyimide resin composition according to this embodiment, a polyimide resin film that can be easily peeled can be formed on various carrier substrates.

  The ratio of the polyamic acid resin or the polyamic acid ester resin to the polyimide resin in the liquid polyimide resin composition is not particularly limited, but is usually 30% or less, preferably 20% or less, and more preferably 10% or less. When 30% or more of the polyamic acid resin or polyamic acid ester resin is contained in the liquid polyimide resin composition, the polyimide resin and the polyamic acid resin or polyamic acid ester resin may be phase-separated to cause white turbidity. is there.

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

  The substance amount of the polyamic acid resin or polyamic acid ester resin in the liquid polyimide resin composition is the weight of the polyamic acid resin or polyamic acid ester resin component contained in the liquid polyimide resin composition represented by the general formula (B1), ( It is obtained by dividing by the average molecular weight of each repeating unit represented by B2) and (B3).

  The substance amount of the polyimide resin in the liquid polyimide resin composition is determined by dividing the weight of the polyimide resin component contained in the liquid polyimide resin composition by the molecular weight of the repeating unit represented by the general formula (1).

  Various methods for measuring the amount of a polyamic acid resin or polyamic acid ester resin in a liquid polyimide resin composition are known, such as nuclear magnetic resonance spectroscopy (NMR) and Fourier transform infrared spectroscopy (FT-IR method). , A method for quantifying moisture accompanying imide ring closure, a method for obtaining by neutralizing titration of carboxylic acid contained in polyamic acid (see JP 2009-269958 A), a specific functional group labeled, and emission intensity or absorption intensity And the like (see Japanese Patent No. 4529760). Various methods for measuring the amount of the polyimide resin in the liquid polyimide resin composition are also known, and examples include nuclear magnetic resonance spectroscopy (NMR) and Fourier transform infrared spectroscopy (FT-IR method). .

  Moreover, in order to control the adhesiveness between the film | membrane obtained by apply | coating a liquid polyimide resin composition to a to-be-coated body, and a to-be-coated body, an additive is added to the liquid polyimide resin composition which concerns on this embodiment. May be added. For example, a coupling agent such as a silane coupling agent or a titanium coupling agent can be added to the liquid polyimide resin composition according to the present embodiment.

  Examples of the silane coupling agent include γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltripropoxysilane, γ-aminopropyltributoxysilane, γ-aminoethyltriethoxysilane, γ -Aminoethyltrimethoxysilane, γ-aminoethyltripropoxysilane, γ-aminoethyltributoxysilane, γ-aminobutyltriethoxysilane, γ-aminobutyltrimethoxysilane, γ-aminobutyltripropoxysilane, and γ- Examples include aminobutyl tributoxysilane.

  Examples of the titanium coupling agent include γ-aminopropyltriethoxytitanium, γ-aminopropyltrimethoxytitanium, γ-aminopropyltripropoxytitanium, γ-aminopropyltributoxytitanium, γ-aminoethyltriethoxytitanium, γ -Aminoethyltrimethoxytitanium, gamma-aminoethyltripropoxytitanium, gamma-aminoethyltributoxytitanium, gamma-aminobutyltriethoxytitanium, gamma-aminobutyltrimethoxytitanium, gamma-aminobutyltripropoxytitanium, and gamma- Examples include aminobutyl tributoxy titanium.

  The liquid polyimide resin composition according to this embodiment may contain one type of coupling agent, or may contain two or more types of coupling agents. The amount of the coupling agent contained in the liquid polyimide resin composition according to this embodiment is preferably 0.1% by mass or more and 3% by mass or less with respect to the polyimide resin from the viewpoint of improving the physical properties of the obtained film. .

  In addition, it is also possible to mix | blend various additives with respect to the liquid polyimide resin composition which concerns 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 the organic filler 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 liquid polyimide resin composition according to this embodiment may be blended. These various fillers and additive components may be added at any stage of any process for producing the polyimide resin.

<1.3 Production method of polyimide resin>
There is no special restriction | limiting in the manufacturing method of the polyimide resin which concerns on this embodiment. As an example, a method for producing a polyamic acid resin or a polyamic acid ester resin, which is a polyimide resin precursor, and converting the obtained precursor into a polyimide resin will be described.

<1.3.1 Production Method of Polyamic Acid Resin>
The polyamic acid resin is obtained by reacting a tetracarboxylic dianhydride represented by the general formula (E1) with a diamine compound represented by the general formula (E2) in an appropriate solvent. ^{R 1} in the general formula (E2) shows the same structure as ^{R 1} in the general formula (2).

  In addition, the polyamic acid ester resin was obtained by diesterifying the tetracarboxylic dianhydride represented by the general formula (E1) by using a ring such as methanol, ethanol, isopropanol, or n-propanol to open the ring. It can be obtained by reacting the diester with a diamine compound represented by the general formula (E2) in an appropriate solvent. 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.

  In the reaction for obtaining a polyamic acid resin or a polyamic acid ester resin, only one diamine compound may be used, or a mixture of two or more diamine compounds may be used.

  The tetracarboxylic dianhydride represented by the general formula (E1) is mixed with other tetracarboxylic dianhydrides to such an extent that the colorlessness, transparency and various physical properties of the polyimide resin according to this embodiment are not impaired. May be. 1 type may be sufficient as the tetracarboxylic dianhydride mixed, and 2 or more types may be sufficient as it.

  The tetracarboxylic dianhydride that may be mixed is not limited as long as the object of the present invention is not impaired. For example, ethylenetetracarboxylic dianhydride, butanetetracarboxylic dianhydride, cyclopentanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 1,2,3,4 -Cyclohexanetetracarboxylic dianhydride, pyromellitic 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, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride 2,2-bis (2,3-dicarboxyphenyl) propane dianhydride, 2,2-bis (3,4-dicarboxyphenyl) -1,1,1,3,3,3-he Safluoropropane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) -1,1,1,3,3,3-hexafluoropropane dianhydride, bis (3,4-dicarboxyphenyl) ) Sulfone dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, bis (2,3-dicarboxyphenyl) ether dianhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic acid Dianhydride, 2,2 ′, 3,3′-benzophenonetetracarboxylic dianhydride, 4,4- (p-phenylenedioxy) diphthalic dianhydride, 4,4- (m-phenylenedioxy) Diphthalic dianhydride, 1,2,5,6-naphthalenedicarboxylic dianhydride, 1,4,5,8-naphthalenedicarboxylic dianhydride, 2,3,6,7-naphthalenedicarboxylic dianhydride , , 2,3,4-benzenetetracarboxylic dianhydride, 2,2 ′, 6,6′-biphenyltetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 2 3,6,7-anthracenetetracarboxylic dianhydride, 1,2,7,8-phenanthrenetetracarboxylic dianhydride, and the like.

  In addition, tetracarboxylic dianhydrides having an aromatic ring such as pyromellitic dianhydride and tetracarboxylic dianhydrides having a rigid skeleton such as 1,2,4,5-cyclohexanetetracarboxylic dianhydride If excessively used, solubility of the resulting polyimide resin in a solvent, colorlessness, transparency, and various physical properties may be impaired.

  The reaction of the tetracarboxylic dianhydride represented by the general formula (E1) and the diamine compound represented by the general formula (E2) can be carried out under 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 polyamic acid resin can be obtained by sequentially adding a tetracarboxylic dianhydride and a diamine compound to a solvent and 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, the yield of the polyamic acid resin obtained can be improved.

  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 weight or more, preferably 5% by weight or more with respect to the total amount of solution, while usually 70%. % By weight or less, preferably 30% by weight or less. 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 reaction temperature is not particularly limited, but is usually 0 ° C. or higher, preferably 20 ° C. or higher, and is usually 100 ° C. or lower, preferably 80 ° C. or lower. The reaction time is not particularly limited, but is usually 1 hour or more, preferably 2 hours or more, while it is usually 100 hours or less, preferably 24 hours or less. 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 in this reaction include hydrocarbon solvents such as hexane, cyclohexane, heptane, benzene, toluene, xylene and mesitylene; carbon tetrachloride, methylene chloride, chloroform, 1,2-dichloroethane, chlorobenzene, dichlorobenzene and fluorobenzene. Halogenated hydrocarbon solvents such as: diethyl ether, tetrahydrofuran, 1,4-dioxane and ether solvents such as methoxybenzene; ketone solvents such as acetone and methyl ethyl ketone; N, N-dimethylformamide, N, N-dimethylacetamide and Amide solvents such as N-methyl-2-pyrrolidone; aprotic polar solvents such as dimethyl sulfoxide; heterocyclic solvents such as pyridine, picoline, lutidine, quinoline and isoquinoline; Phenolic solvents such as 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 represented by the general formula (E1) with the diamine compound represented by the general formula (E2) mainly includes the following general A repeating unit represented by the formula (B1), (B2), or (B3) is included.

In General Formulas (B1), (B2), and (B3), R ² represents a hydrogen atom or an alkyl group having 1 to 14 carbon atoms that may have a substituent. Although there is no special restriction | limiting 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.

  In the polyamic acid resin or polyamic acid ester resin obtained in the present embodiment, a repeating structure represented by the general formula (B1), a repeating structure represented by the general formula (B2), and a repeating structure represented by the general formula (B3) The abundance ratio between and is not particularly limited. The polyimide resin according to the present embodiment is obtained by converting the polyamic acid resin or the polyamic acid ester resin thus obtained into a polyimide resin by a method described later.

<1.3.2 Polyimide resin>
The polyimide resin according to the present embodiment is obtained by subjecting the above-described polyamic acid resin or polyamic acid ester resin to dehydration cyclization or dealcoholization cyclization (hereinafter collectively referred to as dehydration). This cyclization reaction may be performed on a solid polyamic acid resin or polyamic acid ester resin, or may be performed on a solution of a polyamic acid resin or a polyamic acid ester resin. The method of dehydration is not particularly limited, and a conventionally known method can be used. Examples thereof include thermal imidization that causes thermal cyclization and chemical imidization that causes chemical cyclization.

  First, a case where a cyclization reaction is performed on a solid state polyamic acid resin or polyamic acid ester resin will be described. In this case, first, the solvent is distilled off from the polyamic acid resin or polyamic acid ester resin solution obtained by the above-described method. As another method, a polyamic acid resin or a polyamic acid ester resin solution may be added to a solvent having low resin solubility to precipitate a polyamic acid resin or a polyamic acid ester resin solid.

  The heating method in the heating imidization is not particularly limited, and examples thereof include hot air heating, vacuum heating, infrared heating, microwave heating, and heating by contact using a hot plate or a hot roll. In this case, it is preferable to advance imidization by raising the temperature stepwise. The reaction temperature of the heating imidization reaction is not particularly limited, but is usually 100 ° C. or higher, preferably 150 ° C. or higher, and is usually 350 ° C. or lower, preferably 300 ° C. or lower. The reaction time for the heating imidization is not particularly limited, but is usually 30 minutes or longer, preferably 1 hour or longer, and is usually 3 hours or shorter, preferably 2 hours or shorter. By performing the reaction under such conditions, the conversion reaction can be sufficiently advanced while suppressing decomposition of the compound. The reaction atmosphere in heating imidation is not specifically limited, It can carry out under air, an inert gas atmosphere, or a vacuum. It is more preferable to carry out the reaction in an inert gas atmosphere from the viewpoint of more effectively preventing the resulting polyimide resin from being altered.

  The liquid polyimide resin composition according to this embodiment can be prepared by dissolving the solid polyimide resin thus obtained in a desired organic solvent. The solvent for dissolving the polyimide resin according to this embodiment is not particularly limited. Examples thereof include amide solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, and N-methyl-2-pyrrolidone, and aprotic solvents such as dimethyl sulfoxide. Among these, N, N-dimethylformamide, N, N-dimethylacetamide, and N-methyl-2-pyrrolidone are particularly preferable. As the solvent, one kind of substance can be used, or two or more kinds of substances can be mixed and used.

  Then, the method to obtain the polyimide resin which concerns on this embodiment by imidizing polyamic acid resin or polyamic acid ester resin in a solution is demonstrated. The imidization can be performed using any conventionally known method. Hereinafter, an example of the imidization method will be described, but the present invention is not limited to this method.

  A polyimide resin solution can be obtained by heating a solution of a polyamic acid resin or a polyamic acid ester resin. In this case, water (or alcohol) generated by the imidization reaction inhibits the ring closure reaction, and thus is preferably discharged out of the reaction system. 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.

  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.

  The polyimide resin solution thus obtained may be used as it is as the liquid polyimide resin composition according to the present embodiment. Further, for example, by adding a solution in a solvent having low solubility of the polyimide resin, the polyimide resin is precipitated, and by dissolving the precipitated polyimide resin in a desired solvent, the liquid polyimide resin composition according to this embodiment is prepared. May be.

<2. Device Creation Method Using Liquid Polyimide Resin Composition According to this Example>
By using the liquid polyimide resin composition according to this embodiment, a device in which a circuit is formed on a polyimide resin film can be produced. The liquid polyimide resin composition according to this embodiment is suitable for producing a thin device and a flexible device that can be bent. Examples of devices that can be produced according to the following method using the liquid polyimide resin composition according to the present embodiment include display devices such as liquid crystal displays, organic EL displays, and electronic paper, solar cells, and CMOS. Examples include a light receiving device. Below, the device preparation method using the liquid polyimide resin composition which concerns on this embodiment is demonstrated with reference to FIG.

<2.1 (a) Step of forming a polyimide resin film>
The solid polyimide resin film 120 can be formed on the carrier substrate 110 by applying the liquid polyimide resin composition according to the present embodiment on the carrier substrate 110 and drying it by volatilizing the solvent.

  The carrier substrate 110 is preferably hard and heat resistant. That is, it is preferable to use a material that does not deform even when exposed to a temperature required in the manufacturing process. Specifically, the carrier substrate 110 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, preferred examples of the material of the carrier substrate 110 include metals such as glass and stainless steel, or resin films.

  The thickness of the carrier substrate 110 is usually 0.3 mm or more, preferably 0.5 mm or more, and is usually 5.0 mm or less, preferably 3.0 mm or less. When the thickness of the carrier substrate 110 is in such a range, the impact resistance of the carrier substrate 110 can be improved and the device manufacturing cost can be reduced.

  The method for applying the liquid polyimide resin composition according to the present embodiment to the carrier substrate 110 is not particularly limited as long as the method can form a layer having a uniform thickness on the carrier substrate 110. 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.

  A method for volatilizing the solvent is not particularly limited. Usually, the solvent is volatilized by heating the carrier substrate 110 coated with the liquid polyimide resin composition. 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, while usually 300 ° C. or lower, preferably 250 ° C. or lower, more preferably. Is 200 ° C. or lower. When the solvent removal temperature is 40 ° C. or higher, it is preferable in that the solvent is sufficiently volatilized. In addition, when the solvent removal temperature is 200 ° C. or lower, since the organic solvent does not volatilize rapidly, bubbles or the like can be prevented from being generated in the obtained polyimide resin film 120. This is preferable because the possibility of reducing the appearance and quality of the resulting polyimide resin film 120 can be reduced.

  The thickness of the resulting polyimide resin film 120 can be controlled by adjusting the coating amount of the liquid polyimide resin composition. The thickness of the polyimide resin film 120 is usually 1 μm or more, preferably 2 μm or more, and is usually 200 μm or less, preferably 100 μm or less. When the thickness is 1 μm or more, the polyimide resin film 120 can have sufficient strength. This is preferable in that the strength of the obtained device is improved and the device is less likely to be damaged. Moreover, since it becomes possible to make the device 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 resin film 120 is more preferably 2 to 100 μm.

  The thermal expansion coefficient of the obtained polyimide resin film 120 is preferably 100 ppm / K or less, more preferably 70 ppm / K or less in the range of 100 to 200 ° C., and the thermal expansion of the same level as that of the carrier substrate 110. Most preferably it is. When the coefficient of thermal expansion is in such a range, it is possible to prevent the polyimide resin film 120 from being peeled off from the carrier substrate 110 due to a temperature change in the device manufacturing process.

  The polyimide resin film 120 obtained in the present embodiment is transparent, has little coloration, has heat resistance, and can have high mechanical strength. In the present specification, being colorless or transparent means that the transmittance of a light beam at 400 nm is usually 60% or more, preferably 70% or more, particularly preferably 80% or more when formed into a target shape. It means what is. The polyimide resin film 120 obtained in the present embodiment 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 7361-1 is used as the transmittance.

  Further, the yellowness [yellow index (YI)] of the polyimide resin film 120 obtained in the present embodiment when the film thickness is 50 ± 5 μm is usually −10 or more, preferably −5 or more, more preferably -1 or more. On the other hand, it is usually 20 or less, preferably 15 or less, more preferably 10 or less, and further preferably 5 or less.

  If the transparency of the polyimide resin film 120 obtained in this embodiment used as a plastic film substrate is high, a high-performance display device or a light receiving device with high photoelectric conversion efficiency can be manufactured. For example, a see-through device can be manufactured. In addition, when a plastic film substrate is used as a device substrate for an organic EL display, a bottom emission type light extraction structure that is easy to manufacture can be adopted, so that a device for a large size organic EL display can be easily manufactured. Enable. In addition, since a highly transparent plastic film substrate does not affect the original color of the display, a high-performance device can be produced. Furthermore, the polyimide resin film obtained in the present embodiment has little absorption of light having a wavelength suitable for power generation of solar cells. Therefore, when the polyimide resin film obtained in this embodiment is used as a device substrate on the light-receiving surface side of a solar cell, even if it has the same layer configuration as a solar cell using a conventional glass substrate, photoelectric conversion The efficiency is not significantly reduced. In addition, since the polyimide resin film obtained in the present embodiment has less aromatic skeleton, the film (film) itself has better durability against ultraviolet rays than the conventional aromatic polyimide film (film). It is preferable in a certain point.

  The polyimide resin obtained in the present embodiment preferably has a glass transition temperature (Tg) of 150 ° C. or higher, more preferably 200 ° C. or higher, more preferably 250 ° C. or higher. Since the glass transition temperature is high, the heat resistance of the device obtained in the present embodiment can be improved.

  The polyimide resin obtained in this embodiment depends on the type of device to be produced, but preferably has the following mechanical strength. Although there is no special restriction | limiting, the tensile strength of the polyimide resin 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. 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 resin has such mechanical strength, a more durable device can be obtained.

<2.2 (b) Step of forming a circuit on a polyimide resin film>
Next, the circuit 130 is formed on the polyimide resin film 120 formed as described above. The formed circuit 130 differs depending on the type of device. For example, when manufacturing a TFT liquid crystal display device, for example, an amorphous silicon TFT may be formed on the polyimide resin film 120. For example, 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.

  Moreover, when manufacturing a solar cell device, a solar cell using, for example, crystalline silicon, amorphous silicon, a compound semiconductor material, or an organic semiconductor material may be formed on the polyimide resin film 120. 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.

  When the polyimide resin film according to the present embodiment, which is excellent in various properties such as heat resistance and toughness, is used, the circuit 130 can be formed using various methods.

  For the polyimide resin film 120 on which the circuit 130 is formed by this step (b), before performing the step (c) shown below, a sealing process, a process for laminating layers other than the circuit, and a member Other processing such as modularization may be performed.

<2.3 (c) Step of peeling the polyimide resin film on which the circuit is formed from the carrier substrate>
Next, the polyimide resin film 120 having the circuit 130 formed on the surface is peeled from the carrier substrate 110. The peeling method is not particularly limited, and examples thereof include a method of irradiating a laser from the carrier substrate 110 side, a method of immersing in water, a method of physically peeling, and the like. However, the physical peeling method is particularly preferable in that it can be peeled off without impairing the performance of the circuit 130 formed on the polyimide resin film 120. As a method of physically peeling, a method of obtaining a device film by separating the peripheral edge of the circuit on the polyimide resin film on the carrier substrate, a method of obtaining a device film by sucking the peripheral edge of the circuit on the polyimide resin film, a polyimide resin Examples include a method of obtaining a device film by fixing the peripheral edge of a circuit on a film and moving only a carrier substrate.

In order to use such a method, the peel strength between the carrier substrate and the polyimide resin film in a peel test according to JIS K 6854-2 is usually greater than 0 N / m, preferably 0.5 N / m or more, more preferably Is 1.0 N / m or more, more preferably 1.5 N / m or more, and still more preferably 3.0 N / m or more, while usually 5.0 × 10 ³ N / m or less, preferably 3.0 × 10 ³ N / m or less. It is preferable that the peel strength between the carrier substrate and the polyimide resin film is greater than 0 N / m because the polyimide resin film does not peel off or shift from the carrier substrate during circuit formation. On the other hand, when the peeling strength between the carrier substrate and the polyimide resin film is 5.0 × 10 ³ N / m or less, the polyimide resin film is peeled from the carrier substrate without damaging the circuit laminated on the polyimide resin film. Is preferable.

  Further, as a method for measuring peel strength, a cross-cut peel test according to JIS K 5600-5-6 may be used. The ratio of the polyamic acid resin or polyamic acid ester resin to the polyimide resin in the liquid polyimide resin composition to be used is not particularly limited, but is usually 30% or less, preferably 10% or less, more preferably from the viewpoint of peel strength. It is 5% or less, more preferably 1% or less, and particularly preferably 0.75% or less. The definition and measurement method of the ratio of the polyamic acid resin or the polyamic acid ester resin to the polyimide resin in the liquid polyimide resin composition are as described above.

  The polyimide resin film obtained according to this embodiment does not have too strong adhesion to the carrier substrate. Therefore, the polyimide resin film can be peeled off from the carrier substrate without damaging the circuit formed on the polyimide resin film. In particular, the polyimide resin film obtained according to the present embodiment can be easily peeled even when glass, which is inexpensive but may have too strong adhesion to the resin film, is used as the carrier substrate. As described above, according to the method of the present embodiment, a device can be manufactured at a low cost in a shorter process.

  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.

[Transparency measurement]
It measured according to the test method of JISK7361-1 total light transmittance. The total light transmittance at 400 nm was measured using a spectrophotometer (U-4000) manufactured by Hitachi High-Tech. Higher transmittance means better transparency of the film.

[YI value measurement]
It measured according to JISK7103. The yellow index (YI) was measured using a color computer (SM-5) manufactured by Suga Test Instruments.

[Peel strength measurement]
A blue plate glass plate (10 × 20 cm, 3 mm thickness) was used as the carrier substrate, and the blue plate glass plate was washed with a neutral surfactant and distilled water before applying the liquid polyimide resin composition solution. The peel strength in the examples was evaluated by a cross cut test according to JIS K 5600-5-6. The greater the number of cells remaining on the grid after the peel test, the stronger the adhesive strength, that is, the stronger the peel strength. The evaluation of peel strength is shown by the number of squares to which the resin film is adhered after the peel test per 100 squares.

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

１，１’−ビフェニル−３，３’，４，４’−テトラカルボン酸二無水物１５０ｇを水５９３ｇと水酸化ナトリウム８３．３ｇとの溶液に溶解して１，１’−ビフェニル−３，３’，４，４’−テトラカルボン酸四ナトリウム塩の水溶液を作製し、ルテニウム／カーボン触媒を用いて１０ＭＰａＧ、１２０℃で核水素化した。次いで４９％硫酸水溶液４２９ｇを滴下し、析出した固体を濾過することにより、ジシクロヘキシル−３，３’，４，４’−テトラカルボン酸（Ｈ−ＢＴＣ）１５７ｇ（収率８１％）を得た。

1,1′-biphenyl-3,3 ′, 4,4′-tetracarboxylic dianhydride 150 g was dissolved in a solution of 593 g of water and 83.3 g of sodium hydroxide to obtain 1,1′-biphenyl-3, An aqueous solution of 3 ′, 4,4′-tetracarboxylic acid tetrasodium salt was prepared and subjected to nuclear hydrogenation at 10 MPaG and 120 ° C. using a ruthenium / carbon catalyst. Subsequently, 429 g of a 49% sulfuric acid aqueous solution was dropped, and the precipitated solid was filtered to obtain 157 g of dicyclohexyl-3,3 ′, 4,4′-tetracarboxylic acid (H-BTC) (yield 81%).

  The obtained dicyclohexyl-3,3 ′, 4,4′-tetracarboxylic acid (H-BTC) 33.7 g (0.98 mol) was added to a 300 ml three-necked flask equipped with a thermometer, a stirrer, and a Dimroth condenser. And 90 g of acetic anhydride were added under nitrogen. The mixture was heated with stirring and reacted at reflux temperature (130 ° C. to 140 ° C.) for 3 hours. After the reaction, the reaction solution was cooled to 10 ° C., and the solid was filtered to obtain white crystals. The obtained crystals were washed with toluene and dried with a vacuum drier to obtain 1,1′-bicyclohexane-3,3 ′, 4,4′-tetracarboxylic acid-3,3 ′, 4, 23.5 g (yield 78%) of a 4′-dianhydride (H-BPDA) -containing composition was obtained.

<Synthesis Example 2>
(Preparation of polyamic acid ester resin solution)
1,1′-bicyclohexane-3,3 ′, 4,4′-tetracarboxylic acid-3,3 ′, 4,4′-dianhydride (H-BPDA) 12.3 g obtained in Synthesis Example 1 (40.0 mmol) was added to N, N-dimethylacetamide (53.4 g), and the mixture was stirred at room temperature under a nitrogen stream. A solution prepared by dissolving 0.065 g (2.02 mmol) of methanol and 0.0037 g (0.04 mmol) of dimethylaminoethanol in 3.0 g of N, N-dimethylacetamide was added to the reaction solution, and further stirred at 70 ° C. for 2 hours. did. Thereafter, a solution in which 2,2-bis [4- (4-aminophenoxy) phenyl] propane (BAPP, manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved in 23 g of N, N-dimethylacetamide was added to the reaction solution, and the mixture was heated at 70 ° C. The target polyamic acid ester resin solution was obtained by heating and stirring for 2 hours and further at 80 ° C. for 4 hours.

<Synthesis Example 3>
(Creation of liquid polyimide resin composition)
In a four-necked flask equipped with a dry nitrogen gas inlet tube, a condenser, a Dean-Stark agglomerator filled with toluene, and a stirrer, the polyamic acid ester resin solution (50 g) obtained in Synthesis Example 2, 7.5 g of toluene, Triethylamine 0.09g was put and the inside of a 4-neck flask was made into nitrogen atmosphere. It heated to 190 degreeC and the water generated with imidation was distilled off azeotropically with toluene. When heating and refluxing and stirring were continued for 6 hours, generation of water was not observed. Subsequently, heating was performed for 1 hour while distilling off toluene and triethylamine to obtain a liquid polyimide resin composition.

<Example 1>
The polyimide resin adhered to the glass plate by casting the liquid polyimide resin composition obtained in Synthesis Example 3 to a thickness of 100 μm on the glass plate using a film applicator and drying at 80 ° C. for 30 minutes under reduced pressure. A membrane was created. About the obtained polyimide resin film, transparency, YI value, and peeling strength were measured according to the method as described above. The evaluation results are shown in Table 1.

<Example 2>
In the polyamic acid ester resin solution obtained in Synthesis Example 2 and Synthesis Example 3 so that the ratio of the polyamic acid resin or the polyamic acid ester resin to the polyimide resin in the liquid polyimide resin composition solution is 0.2%. The obtained liquid polyimide resin composition was mixed to prepare a liquid polyimide resin composition solution. The obtained liquid polyimide resin composition solution is cast on a glass plate with a thickness of 100 μm using a film applicator, and dried at 80 ° C. for 30 minutes under reduced pressure to create a polyimide resin film adhered to the glass plate. did. About the obtained polyimide resin film, transparency, YI value, and peeling strength were measured according to the method as described above. The evaluation results are shown in Table 1.

<Example 3>
In Example 2, the polyamic acid ester resin solution and the liquid polyimide resin composition were mixed so that the ratio of the polyamic acid resin or the polyamic acid ester resin to the polyimide resin in the liquid polyimide resin composition solution was 1%. Then, a polyimide resin film was prepared in the same manner as in Example 2 except that a liquid polyimide resin composition solution was prepared. About the obtained polyimide resin film, transparency, YI value, and peeling strength were measured according to the method as described above. The evaluation results are shown in Table 1.

<Comparative Example 1>
The polyamic acid ester resin solution obtained in Synthesis Example 2 was cast on a glass plate with a thickness of 100 μm using a film applicator, and dried under reduced pressure at 80 ° C. for 30 minutes. After drying, a polyimide resin film adhered to a glass plate was prepared by heating at 230 ° C. for 1 hour and further at 300 ° C. for 1 hour in a nitrogen atmosphere. The polyamic acid ester resin is converted into a polyimide resin by heating. About the obtained polyimide resin film, transparency, YI value, and peeling strength were measured according to the method as described above. The evaluation results are shown in Table 1.

  As shown in Table 1, the polyimide resin films obtained in Examples 1 to 3 exhibit better peelability than the polyimide resin film obtained in Comparative Example 1. Moreover, adhesiveness can be controlled with the quantity of the polyamic acid ester added with respect to a liquid polyimide resin composition so that Examples 1-3 may show.

110 Carrier substrate 120 Polyamide resin film 130 Circuit

Claims (3)

Forming a solid polyimide resin film on the carrier substrate by applying and drying the liquid polyimide resin composition on the carrier substrate;
Forming a circuit on the polyimide resin film;
Peeling the polyimide resin film on which the circuit is formed from the carrier substrate;
A device manufacturing method comprising:
The said liquid polyimide resin composition contains the polyimide resin containing the repeating unit represented by following formula (1), and a solvent, The device manufacturing method characterized by the above-mentioned.

(In formula (1), R ¹ represents a divalent organic group.) The device manufacturing method according to claim 1, wherein R ¹ is an organic group represented by the following formula (2).

(In Formula (2), each of ring A and ring B independently represents an aromatic ring which may have a substituent or an aliphatic ring which may have a substituent, and p and q are Each independently represents an integer of 0 to 10. X represents 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 optionally having —, —NH—, or —O—C _n H _2n —O— (n is an integer of 1 to 5) Y ¹ and Y ² are each independently and directly A 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, and when p or q is 2 or more, a plurality of Y ¹ or Y ² may be different from each other.)   The device manufacturing method according to claim 1, wherein the polyimide resin film has a total light transmittance at 400 nm of 70% or more according to JIS K 7361-1.

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