TW201920579A - Composition for forming temporary bonding layer, and temporary bonding layer - Google Patents

Abstract

A composition for forming a temporary bonding layer, which is used for the purpose of forming a temporary bonding layer that affixes a resin substrate onto a base material, and which contains (A) a polyamic acid of formula (P1), (B) a polyamic acid of formula (P2), (C) a silane coupling agent having an amino group or the like, and (D) a mixed solvent that contains an amide-based solvent or the like. (In formula (P1), X1 represents a divalent aromatic group having two carboxy groups and an ester bond, or the like; and Y1 represents a divalent aromatic group having an ester bond, or the like.) (In formula (P2), X2 represents a divalent aromatic group having two carboxy groups and an ether bond, or the like; and Y2 represents a divalent aromatic group having an ether bond, or the like).

Description

Composition for temporary bonding layer formation and temporary bonding layer

The present invention relates to a composition for forming a temporary adhesive layer and a temporary adhesive layer.

In recent years, in addition to the characteristics of thinness and weight reduction of electronic devices, it is required to provide a flexible function. Therefore, in order to replace the conventional heavy, fragile, and inflexible glass substrates, lightweight flexible plastic substrates are required.

Especially for the new generation display, it is required to develop an active matrix full-color TFT display panel using a lightweight flexible plastic substrate (hereinafter referred to as a resin substrate). In addition, as for the touch panel type display, there have been developed materials that are compatible with flexible materials such as transparent electrodes or resin substrates of the touch panel used in combination with the display panel. As for transparent electrodes, ITO has been used conventionally, and other transparent electrode materials such as PEDOT that can be bended, such as transparent conductive polymers, metal nanowires, and hybrid systems have been proposed (see Patent Documents 1 to 4). .

On the other hand, the substrate of the film used in the touch panel display is also replaced by glass to a sheet made of plastic such as polyethylene terephthalate, polyimide, cycloolefin polymer resin, and acrylic resin. , And developed a flexible transparent touch screen panel (Patent Documents 5 to 6).

In general, in order to stably produce a flexible touch screen panel, an adhesive layer is formed on a supporting substrate such as a glass substrate, and after a device is fabricated thereon, the device is produced by peeling the device from the adhesive layer ( Patent Document 7). This adhesive layer cannot be peeled off during the manufacturing steps of the panel as described above. On the other hand, it needs to have a moderate peeling force when peeling. It is also important that when the touch screen panel is fabricated on the substrate and peeled off, there is no change in the peeling force before and after the manufacturing process of the device.
[Prior technical literature]
[Patent Literature]

[Patent Document 1] International Publication No. 2012/147235
[Patent Document 2] Japanese Patent Laid-Open No. 2009-283410
[Patent Document 3] Japanese Patent Publication No. 2010-507199
[Patent Document 4] Japanese Patent Laid-Open No. 2009-205924
[Patent Document 5] International Publication No. 2017/002664
[Patent Document 6] Japanese Patent Laid-Open No. 2015-166145
[Patent Document 7] Japanese Patent Laid-Open No. 2016-531358

[Problems to be Solved by the Invention]

The present invention has been made in view of the above-mentioned circumstances, and it is an object of the present invention to provide a composition for forming a temporary adhesive layer that can provide a temporary adhesive layer. The temporary adhesive layer has a resin substrate formed on a substrate in the process of manufacturing an electronic device. Appropriate adhesion, excellent heat resistance and solvent resistance to a degree that does not peel off, and small change in the peeling force before and after the manufacturing process of electronic devices such as touch panel sensors, can exhibit stable adhesion.

[Means for solving problems]

As a result of intensive research conducted by the inventors of the present case to solve the above-mentioned problems, it was found that a polyamic acid having an ester bond and a polyamic acid having an ether bond are used in combination, and a silane coupling agent having an amine group or a urea group is combined, and The composition of a mixed solvent of a predetermined organic solvent can provide excellent adhesion to a substrate, moderate adhesion to a resin substrate, moderate peelability, and excellent heat resistance. A hardened film with a small change and capable of exhibiting stable adhesiveness has completed the present invention.

That is, the present invention provides the following composition for forming a temporary adhesive layer and a temporary adhesive layer:
1. A composition for temporarily adhering a layer, which is used for forming an electronic device on a resin substrate laminated on the surface of a substrate, and is interposed between the substrate and the resin substrate to form and fix the resin substrate on the substrate. The composition of the temporary adhesion layer on the above substrate is characterized by:
It contains: (A) a polyamic acid represented by the following formula (P1), (B) a polyamino acid represented by the following formula (P2), (C) a silane coupling agent having an amine group or a urea group And (D) a mixed solvent containing two or more kinds selected from a amine-based solvent, an ester-based solvent, an ether-based solvent, and an alcohol-based solvent,
It provides that the peeling force from the substrate is higher than the peeling force from the resin substrate, and the peeling force from the resin substrate is 0.1 to 0.3 N / 25 mm before the electronic device is manufactured, and during the manufacturing of the electronic device, The temporary bonding layer is 0.1 ～ 0.3N / 25mm;

(In the formula, X ¹ represents a divalent aromatic group having two carboxyl groups and an ester bond, or a divalent aromatic group having two carboxyl groups and no ester bond; Y ¹ represents a divalent aromatic group having an ester bond. Or a divalent aromatic group without an ester bond, at least one of X ¹ and Y ¹ is an aromatic group with an ester bond, and m represents a natural number)

(In the formula, X ² represents a divalent aromatic group having two carboxyl groups and an ether bond, or a divalent aromatic group having two carboxyl groups and no ether bond; Y ² represents a divalent aromatic group having an ether bond. Or a divalent aromatic group having no ether bond, at least one of X ² and Y ² is an aromatic group having an ether bond, and n represents a natural number).
2. The composition for forming a temporary adhesive layer according to 1, wherein X ¹ is an aromatic group represented by the following formula (1) or (2):
.
3. The composition for forming a temporary adhesive layer according to 1 or 2, wherein X ² is an aromatic group represented by the following formula (3):
.
4. The composition for forming a temporary adhesive layer according to any one of 1 to 3, wherein the Y ¹ is an aromatic group represented by any one of the following formulae (4) to (6):
.
5. The composition for forming a temporary adhesive layer according to any one of 1 to 4, wherein the Y ² is an aromatic group represented by the following formula (7) or (8):
.
6. The composition for forming a temporary adhesive layer according to any one of 1 to 5, wherein one or both of the component (A) and the component (B) is a polyamic acid having an amine group at both ends.
7. The composition for forming a temporary adhesive layer according to any one of 1 to 6, wherein the blending mass ratio of the component (A) to the component (B) is (A): (B) = 2: 8 to 8: 2.
8. The composition for forming a temporary adhesive layer according to any one of 1 to 7, wherein the component (C) is aminopropyltrimethoxysilane, and its content is relative to the total of the components (A) and (B) The mass is less than 5 mass%.
9. The composition for forming a temporary adhesive layer according to any one of 1 to 8, wherein the component (D) is a mixed solvent containing one or more organic solvents selected from the amidine-based solvents.
10. A temporary adhesive layer formed using the composition for forming a temporary adhesive layer according to any one of 1 to 9.
11. The temporary adhesive layer of 10, whose glass transition temperature is less than 300 ° C.
12. A laminated body formed by forming a resin layer having a light transmittance of 450% or more at a wavelength of 450 nm on a temporary adhesive layer such as 10 or 11.
13. A method for manufacturing an electronic device, comprising:
A step of applying the composition for forming a temporary adhesive layer according to any one of 1 to 9 on a substrate to form a temporary adhesive layer;
A step of forming a resin substrate having a light transmittance of more than 80% at a wavelength of 450 nm on the temporary adhesive layer;
A step of manufacturing an electronic device on the resin substrate; and a step of peeling the resin substrate with a peeling force of 0.1 to 0.3 N / 25 mm.

[Effect of the invention]

By using the composition for forming a temporary adhesive layer of the present invention, it is possible to obtain reproducibly excellent adhesion to a substrate, moderate adhesion to a resin substrate, moderate peelability, and excellent heat resistance. The change of the peeling force before and after the manufacturing process of the device is small, and the temporary bonding layer can exhibit stable adhesiveness. In addition, in the manufacturing process of the electronic device, the resin substrate can be separated from the substrate at the same time as the circuit and the like without causing damage to a resin substrate formed on the substrate or a circuit further provided thereon. Therefore, the composition for forming a temporary adhesive layer of the present invention can contribute to speeding up a process of an electronic device provided with a resin substrate, improvement in yield, and the like.

[Form of Implementing Invention]

The composition for forming a temporary adhesive layer of the present invention contains the following components (A) to (D).

In the present invention, the temporary bonding layer refers to a layer provided directly above a substrate (glass substrate, etc.) for forming a resin substrate, and is used to fix the resin substrate to the substrate when a resin substrate having no adhesive force to the substrate is formed. Layer on top. As a typical example, in the process of manufacturing a flexible electronic device, in order to fix the resin substrate to the above-mentioned substrate in a predetermined process, and the flexibility made of a resin such as polyimide resin or acrylic resin is mentioned. A temporary bonding layer is provided between resin substrates of an electronic device, and after an electronic circuit or the like is formed on the resin substrate, the resin substrate can be easily peeled from the substrate.

(A) Ingredient
(A) The component is a polyamic acid represented by the following formula (P1):
.

In formula (P1), X ¹ represents a divalent aromatic group having two carboxyl groups and an ester bond, or a divalent aromatic group having two carboxyl groups and no ester bond; Y ¹ represents a divalent aromatic group having an ester bond Group, or a divalent aromatic group having no ester bond, and at least one of X ¹ and Y ¹ is an aromatic group having an ester bond. m represents a natural number, and is preferably an integer of 2 or more.

In the above X ¹ , as the divalent aromatic group having two carboxyl groups, a divalent aromatic ring containing 1 to 5 benzene rings is preferable, and a divalent benzene ring, a divalent naphthalene ring, and a divalent link are more preferable. The benzene ring is more preferably a divalent benzene ring and a divalent biphenyl ring. The divalent aromatic group having an ester bond and two carboxyl groups is preferably an aromatic group represented by the following formula (1) or (2).

As a divalent aromatic group having two carboxyl groups and not having an ether bond, an aromatic group represented by the following formula (3) is preferable, and the following formula (3 ') or (3 "is preferable ) Is an aromatic group.

In the above Y ¹ , the divalent aromatic group is preferably an aromatic group containing 1 to 5 benzene rings. The divalent aromatic group having no ester bond is more preferably a divalent benzene ring and a divalent biphenyl ring, and more preferably an aromatic group represented by the following formulae (4) and (5). The divalent aromatic group having an ester bond is preferably an aromatic group represented by the following formula (6).

The polyamic acid represented by the formula (P1) can be obtained by reacting the following aromatic tetracarboxylic dianhydride component with an aromatic diamine component.

[Aromatic tetracarboxylic dianhydride component]
As the aromatic tetracarboxylic dianhydride component, an aromatic tetracarboxylic dianhydride having an ester bond or an aromatic tetracarboxylic dianhydride having no ester bond is used.

The above-mentioned aromatic tetracarboxylic dianhydride having an ester bond contains an ester bond in its molecule. Examples of such an aromatic tetracarboxylic dianhydride include a tetracarboxylic dianhydride having a structure in which a plurality of aromatic rings having 6 to 20 carbon atoms are connected by an ester bond. Specific examples of the aromatic ring include a benzene ring, a naphthalene ring, a biphenyl ring, and the like, and a benzene ring and a biphenyl ring are preferred. Among these, from the viewpoint of ensuring the solubility of polyamic acid in an organic solvent, a structure having three or four aromatic rings connected by an ester bond is preferred.

In the present invention, preferable specific examples of the aromatic tetracarboxylic dianhydride having an ester bond include the followings.

The aromatic tetracarboxylic dianhydride having no ester bond is preferably one containing 1 to 5 benzene rings, and more preferably one containing a benzene skeleton, a naphthyl skeleton, or a biphenyl skeleton.

Specific examples of the aromatic tetracarboxylic dianhydride having no ester bond include pyromellitic dianhydride, benzene-1,2,3,4-tetracarboxylic dianhydride, and naphthalene-1,2, 3,4-tetracarboxylic dianhydride, naphthalene-1,2,5,6-tetracarboxylic dianhydride, naphthalene-1,2,6,7-tetracarboxylic dianhydride, naphthalene-1,2,7, 8-tetracarboxylic dianhydride, naphthalene-2,3,5,6-tetracarboxylic dianhydride, naphthalene-2,3,6,7-tetracarboxylic dianhydride, naphthalene-1,4,5,8- Tetracarboxylic dianhydride, biphenyl-2,2 ', 3,3'-tetracarboxylic dianhydride, biphenyl-2,3,3', 4'-tetracarboxylic dianhydride, biphenyl-3,3 ', 4,4'-tetracarboxylic dianhydride, anthracene-1,2,3,4-tetracarboxylic dianhydride, anthracene-1,2,5,6-tetracarboxylic dianhydride, anthracene-1,2 , 6,7-tetracarboxylic dianhydride, anthracene-1,2,7,8-tetracarboxylic dianhydride, anthracene-2,3,6,7-tetracarboxylic dianhydride, phenanthrene-1,2,3 , 4-tetracarboxylic dianhydride, phenanthrene-1,2,5,6-tetracarboxylic dianhydride, phenanthrene-1,2,6,7-tetracarboxylic dianhydride, phenanthrene-1,2,7,8 -Tetracarboxylic dianhydride, phenanthrene-1,2,9,10-tetracarboxylic dianhydride, phenanthrene-2,3,5,6-tetracarboxylic dianhydride, phenanthrene-2,3,6,7-tetracarboxylic acid Carboxylic dianhydride, phenanthrene-2,3,9,10-tetracarboxylic dianhydride, phenanthrene-3,4,5,6-tetracarboxylic dianhydride, phenanthrene-3,4,9,10-tetracarboxylic acid Dianhydride, 3,3 ', 4,4'-benzophenone tetracarboxylic acid, 3,3', 4,4'-diphenyl ether tetracarboxylic acid, 3,3 ', 4,4'- Phenylphosphonium tetracarboxylic acid, 3,4-dicarboxyl-1,2,3,4-tetrahydro-1-naphthalenesuccinic acid, 2,2-bis (3,4-dicarboxyphenyl) hexafluoroisoprene Propyl, 4,4'-hexafluoroisopropylidene diphthalic acid, etc. These can be used alone or in combination of two or more.

[Aromatic diamine component]
As the aromatic diamine component, an aromatic diamine having an ester bond or an aromatic diamine having no ester bond is used.

The above-mentioned aromatic diamine having an ester bond contains an ester bond in its molecule. Examples of such an aromatic diamine include a diamine having a structure in which a plurality of aromatic rings having 6 to 20 carbon atoms are connected by an ester bond. Specific examples of the aromatic ring include a benzene ring, a naphthalene ring, an anthracene ring, and a phenanthrene ring. Among these, from the viewpoint of ensuring the solubility of polyamic acid in an organic solvent, a diamine having a structure in which two or three aromatic rings are connected by an ester bond is preferred.

As a preferable specific example of the said aromatic diamine which has an ester bond, the following is mentioned.

The above-mentioned aromatic diamine having no ester bond is preferably one containing 1 to 5 benzene rings, and more preferably one containing a benzene skeleton, a naphthyl skeleton, or a biphenyl skeleton.

Specific examples thereof include 1,4-diaminobenzene (p-phenylenediamine), 1,3-diaminobenzene (m-phenylenediamine), and 1,2-diaminobenzene (o-phenylenediamine) Amine), 2,4-diaminotoluene, 2,5-diaminotoluene, 2,6-diaminotoluene, 4,6-dimethyl-m-phenylenediamine, 2,5-dimethyl -P-phenylenediamine, 2,6-dimethyl-p-phenylenediamine, 2,4,6-trimethyl-1,3-phenylenediamine, 2,3,5,6-tetramethyl-p Diamines containing 1 benzene ring, such as phenylenediamine, m-xylene diamine, p-xylene diamine; 1,2-naphthalenediamine, 1,3-naphthalenediamine, 1,4-naphthalenediamine, 1 1,5-naphthalenediamine, 1,6-naphthalenediamine, 1,7-naphthalenediamine, 1,8-naphthalenediamine, 2,3-naphthalenediamine, 2,6-naphthalenediamine, 4,4 '-Biphenyldiamine, 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 3,3'-dicarboxy-4,4'-diaminodiphenylmethane, 3,3 ', 5,5'-tetramethyl-4,4'-diaminodiphenylmethane, 4,4'-diaminobenzidineaniline, 3,3'-dichlorobenzidine, 3,3'-dimethylbenzidine, 2,2'-dimethylbenzidine, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 4, 4'-diaminodiphenylmethane, 2,2-bis (3-aminophenyl) propane, 2,2-bis ( 4-aminophenyl) propane, 3,3'-diaminodiphenylsulfene, 3,4'-diaminodiphenylsulfene, 4,4'-diaminodiphenylsulfene And other diamines containing 2 benzene rings; 1,5-diaminoanthracene, 2,6-diaminoanthracene, 9,10-diaminoanthracene, 1,8-diaminophenanthrene, 2,7- Diaminophenanthrene, 3,6-diaminophenanthrene, 9,10-diaminophenanthrene, 1,3-bis (3-aminophenyl) benzene, 1,3-bis (4-aminophenyl) ) Benzene, 1,4-bis (3-aminophenyl) benzene, 1,4-bis (4-aminophenyl) benzene, 1,3-bis (3-aminophenylsulfide) benzene, 1,3-bis (4-aminophenylsulfide) benzene, 1,4-bis (4-aminophenylsulfide) benzene, 1,3-bis (3-aminophenylsulfonium) benzene, 1,3-bis (4-aminophenylphosphonium) benzene, 1,4-bis (4-aminophenylphosphonium) benzene, 1,3-bis [2- (4-aminophenyl) isopropyl Phenyl] benzene, 1,4-bis [2- (3-aminophenyl) isopropyl] benzene, 1,4-bis [2- (4-aminophenyl) isopropyl] benzene, etc. contain 3 Diamines such as benzene rings are not limited to these. In the present invention, among these, p-phenylenediamine is particularly preferably used. These can be used alone or in combination of two or more.

Further, in the present invention, in order to obtain the above-mentioned polyamic acid (P1), a component having an ester bond is selected from at least one of the tetracarboxylic dianhydride component and a diamine component, and an ester bond is preferably used. Four carboxylic dianhydride ingredients. In addition, the polyamic acid (P1) obtained by reacting the tetracarboxylic dianhydride component with a diamine component is preferably one having amine groups at both ends from the viewpoint of exhibiting desired adhesiveness.

By reacting the aromatic diamine component and the aromatic tetracarboxylic dianhydride component described above, the polyamic acid (P1) of the component (A) can be obtained.

[Organic solvent (reaction solvent)]
The organic solvent (reaction solvent) used for the reaction of the aromatic diamine component and the aromatic tetracarboxylic dianhydride component is not particularly limited as long as it does not adversely affect the reaction, and specific examples include m-formyl Phenol, 2-pyrrolidone, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-vinyl-2-pyrrolidone, N, N-dimethylacetamidine Amine, N, N-dimethylformamide, 3-methoxy-N, N-dimethylpropanamide, 3-ethoxy-N, N-dimethylpropanamide, 3-propane Oxy-N, N-dimethylpropanamide, 3-isopropoxy-N, N-dimethylpropanamide, 3-butoxy-N, N-dimethylpropanamide, 3 -Secondary butoxy-N, N-dimethylpropanamide, 3-tertiary butoxy-N, N-dimethylpropanamide, γ-butyrolactone and the like. The organic solvents may be used alone or in combination of two or more.

In particular, the organic solvent used for the reaction is preferably selected from the sulfonamides represented by the formula (S1) and the (S2) from the viewpoint of sufficiently dissolving the diamine and the tetracarboxylic dianhydride and the polyamic acid. At least one of amidines and amidines represented by formula (S3).

In the formula, R ¹ and R ² each independently represent an alkyl group having 1 to 10 carbon atoms. R ³ represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. a represents a natural number, preferably 1 to 3, and more preferably 1 or 2.

Examples of the alkyl group having 1 to 10 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, secondary butyl, tertiary butyl, n-pentyl, and n-hexane. Base, n-heptyl, n-octyl, n-nonyl, n-decyl and the like. Among these, an alkyl group having 1 to 3 carbon atoms is preferred, and an alkyl group having 1 or 2 carbon atoms is more preferred.

The reaction temperature may be appropriately set in a range from the melting point to the boiling point of the solvent used, and is usually about 0 to 100 ° C; in order to prevent the fluorination in the obtained polyamic acid solution, the polyamine unit is maintained at a high level. The content is preferably about 0 to 70 ° C, more preferably about 0 to 60 ° C, and even more preferably about 0 to 50 ° C.

The reaction time depends on the reaction temperature or the reactivity of the starting materials, and cannot be generalized, but is usually about 1 to 100 hours.

According to the method described above, a target reaction solution containing polyamic acid can be obtained.

The weight average molecular weight of the polyamic acid is preferably 5,000 to 1,000,000, more preferably 10,000 to 500,000, and from the viewpoint of handling properties, still more preferably 15,000 to 200,000. In addition, the weight average molecular weight in the present invention is an average molecular weight obtained by gel permeation chromatography (GPC) analysis and conversion in terms of standard polystyrene.

In the present invention, in general, the reaction solution can be filtered, and the filtrate can be directly or diluted or concentrated to obtain a solution, and this solution can be used to prepare the composition for forming a temporary adhesive layer of the present invention. In this way, not only the mixing of impurities can be reduced, but the adhesiveness, peelability, and the like of the obtained temporary adhesive layer may be deteriorated, and a composition for forming a temporary adhesive layer can be effectively obtained.

The blending amount of the component (A) is preferably 3 to 20% by mass, and more preferably 5 to 20% by mass in the composition. When the blending amount of the component (A) is equal to or less than the upper limit of the above range, the required adhesiveness can be obtained. In addition, by setting the blending amount of the component (A) to be greater than or equal to the lower limit of the above range, it is possible to obtain appropriate adhesion to the resin substrate and appropriate peelability after the device is manufactured.

(B) Ingredient
(B) The component is a polyamic acid represented by the following formula (P2):
.

In the formula (P2), X ² represents a divalent aromatic group having two carboxyl groups and an ether bond, or a divalent aromatic group having two carboxyl groups and no ether bond; Y ² represents a divalent aromatic group having an ether bond Group, or a divalent aromatic group having no ether bond, and at least one of X ² and Y ² is an aromatic group having an ether bond. n represents a natural number, and is preferably an integer of 2 or more.

In the above X ² , as the divalent aromatic group having an ether bond and two carboxyl groups, an aromatic group represented by the following formula (3a) or (3b) is preferable, and the formula (3a ') or ( 3b ').

As the divalent aromatic group having two carboxyl groups and not having an ether bond, the same as those exemplified in the above X ¹ as the divalent aromatic group having two carboxyl groups and not having an ester bond are preferred. An aromatic group represented by the following formula (3), more preferably an aromatic group represented by the following formula (3 ') or (3 ").

In the above Y ² , the divalent aromatic group is preferably an aromatic group containing 1 to 5 benzene rings. The divalent aromatic group having no ether bond is the same as that exemplified in the above Y ¹ as the divalent aromatic group having no ester bond, more preferably a divalent benzene ring and a divalent biphenyl ring, and more preferably An aromatic group represented by the following formulae (4) and (5).

The divalent aromatic group having an ether bond is preferably an aromatic group represented by the following formula (7) or (8).

The polyamic acid represented by the formula (P2) can be obtained by reacting the following aromatic tetracarboxylic dianhydride component with an aromatic diamine component.

[Aromatic tetracarboxylic dianhydride component]
As the aromatic tetracarboxylic dianhydride component, an aromatic tetracarboxylic dianhydride having an ether bond or an aromatic tetracarboxylic dianhydride having no ether bond is used.

The above-mentioned aromatic tetracarboxylic dianhydride having an ether bond contains an ether bond in its molecule. Examples of such an aromatic tetracarboxylic dianhydride include a tetracarboxylic dianhydride having a structure in which a plurality of aromatic rings having 6 to 20 carbon atoms are connected by an ether bond. Specific examples of the aromatic ring include a benzene ring, a naphthalene ring, a biphenyl ring, and the like, and a benzene ring and a biphenyl ring are preferred. Among them, from the viewpoint of ensuring the solubility of polyamic acid in an organic solvent, a structure having three or four aromatic rings connected by an ether bond is preferred.

Preferred examples of the aromatic tetracarboxylic dianhydride having an ether bond in the present invention include the following.

The above-mentioned aromatic tetracarboxylic dianhydride having no ether bond is preferably one containing 1 to 5 benzene rings, and more preferably one containing a benzene skeleton, a naphthyl skeleton or a biphenyl skeleton. As a preferable specific example, the same thing as the example illustrated in the said aromatic tetracarboxylic dianhydride which does not have an ester bond is mentioned.

[Aromatic diamine component]
As the aromatic diamine component, at least one of an aromatic diamine having an ether bond and an aromatic diamine having no ether bond is used.

The above-mentioned aromatic diamine having an ether bond contains an ether bond in its molecule. Examples of such an aromatic diamine include a diamine having a structure in which a plurality of aromatic rings having 6 to 20 carbon atoms are connected by an ether bond. Specific examples of the aromatic ring include a benzene ring, a naphthalene ring, an anthracene ring, and a phenanthrene ring. Among these, from the viewpoint of ensuring the solubility of polyamic acid in an organic solvent, a diamine having a structure in which two or three aromatic rings are connected by an ether bond is preferred.

Specific examples of the above-mentioned aromatic diamine having an ether bond include the following.

The aromatic diamine having no ether bond is preferably one containing 1 to 5 benzene rings, and more preferably one containing a benzene skeleton, a naphthyl skeleton, or a biphenyl skeleton. As a preferable specific example, the same thing as the example illustrated in the said aromatic diamine which does not have an ester bond is mentioned.

In addition, in the present invention, in order to obtain the above-mentioned polyamic acid (P2), a component having an ether bond is selected from at least one of the tetracarboxylic dianhydride component and a diamine component, and an ether bond is more preferably used. The diamine component. In addition, in the present invention, the polyamic acid (P2) obtained by reacting the tetracarboxylic dianhydride component of the (B) component with a diamine component is based on the viewpoint of exhibiting desired adhesiveness. It is preferable to have an amine group at the terminal. Furthermore, in the present invention, it is preferred that the (A) component and the (B) component are both polyamines having amine groups at both ends; more preferably, both components have amine groups at both ends. Polyamidic acid.

By reacting the aromatic diamine component and the aromatic tetracarboxylic dianhydride component described above, the polyamic acid (P2) of the component (B) can be obtained.

The organic solvent (reaction solvent) used for the reaction of the aromatic diamine component and the aromatic tetracarboxylic dianhydride component can be the same as those exemplified above.

The reaction temperature may be appropriately set in a range from the melting point to the boiling point of the solvent used, and is usually about 0 to 100 ° C; in order to prevent the fluorination in the obtained polyamic acid solution, the polyamine unit is maintained high The content is preferably about 0 to 70 ° C, more preferably about 0 to 60 ° C, and even more preferably about 0 to 50 ° C.

The reaction time depends on the reaction temperature or the reactivity of the starting materials, and cannot be generalized, but is usually about 1 to 100 hours.

According to the method described above, a target reaction solution containing polyamic acid can be obtained.

The weight average molecular weight of the polyamic acid is preferably 5,000 to 1,000,000, more preferably 10,000 to 500,000, and from the viewpoint of handling properties, still more preferably 15,000 to 200,000. In addition, the weight average molecular weight in the present invention is an average molecular weight obtained by gel permeation chromatography (GPC) analysis and conversion in terms of standard polystyrene.

In the present invention, in general, the reaction solution can be filtered, and the filtrate can be directly or diluted or concentrated to obtain a solution, and this solution can be used to prepare the composition for forming a temporary adhesive layer of the present invention. In this way, not only the mixing of impurities can be reduced, but the adhesiveness, peelability, and the like of the obtained temporary adhesive layer may be deteriorated, and a composition for forming a temporary adhesive layer can be effectively obtained.

The blending amount of the component (B) is preferably 20 to 40% by mass, and more preferably 25 to 40% by mass in the composition. By setting the blending amount of the component (B) to be equal to or less than the upper limit of the above range, it is possible to obtain appropriate adhesion to the resin substrate and appropriate peelability after the device is manufactured. In addition, by setting the blending amount of the component (B) to be not less than the lower limit of the above range, the required adhesiveness can be obtained.

In addition, the blending ratio of the component (A) and the component (B) is preferably (A) :( B) = 2: 8 to 8: 2, more preferably 2: 8 to 7: 3 in terms of mass ratio. It is more preferably 2: 8 to 5: 5. By setting the blending ratio of the component (A) and the component (B) to the above range, the required adhesiveness can be exhibited.

(C) component From the viewpoint of improving the adhesion, the composition of the present invention is preferably a component (C) containing a silane coupling agent having an amine group or a urea group. As a preferable example of the said silane coupling agent, the silane compound represented by Formula (C1) is mentioned.

In the formula (C1), R ¹¹ represents a methyl group or an ethyl group. X represents a hydrolyzable group. Y represents an amine group or a ureido group. c is an integer from 0 to 3. d is an integer from 0 to 3.

Examples of the hydrolyzable group represented by X include a halogen atom, an alkoxy group having 1 to 3 carbon atoms, and an alkoxyalkoxy group having 2 to 4 carbon atoms. Examples of the halogen atom include a chlorine atom and a bromine atom. The alkoxy group having 1 to 3 carbon atoms is preferably a linear or branched one, and specifically, methoxy, ethoxy, n-propoxy, and isopropoxy. The alkoxyalkoxy group having 2 to 4 carbon atoms is specifically a methoxymethoxy group, a 2-methoxyethoxy group, an ethoxymethoxy group, and a 2-ethoxyethoxy group.

Specific examples of the silane coupling agent include 3-aminopropyltrichlorosilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, and 3-aminopropyl Methylmethyldimethoxysilane, 3-aminopropylmethyldiethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, and the like. In the present invention, 3-aminopropyltrimethoxysilane and 3-ureidopropyltrimethoxysilane are preferred, and 3-aminopropyltrimethoxysilane is more preferred. As the silane coupling agent, a commercially available product can be used.

The blending amount of the component (C) is preferably 0.01 to 5% by mass, and more preferably 0.05 to 3% by mass in the composition. When the blending amount of the component (C) is equal to or less than the upper limit of the above range, good storage stability can be obtained. Moreover, by making (C) component into more than the lower limit of the said range, the required adhesiveness can be acquired.

The blending amount of the component (C) is preferably less than 5% by mass based on the total mass of the components (A) and (B). By setting the blending amount of the component (C) to the above range, desired adhesiveness can be exhibited.

(D) Ingredient
The component (D) is a mixed solvent containing two or more kinds selected from a amine-based solvent, an ester-based solvent, an ether-based solvent, and an alcohol-based solvent. In the present invention, the combination of these solvents is not particularly limited, and a plurality of organic solvents may be combined from the same series of organic solvents as exemplified above, or one or more kinds of organic solvents may be combined from each other. In the present invention, from the viewpoint of coatability, it is preferred to include one or more amine solvents, more preferably a combination of amine solvents and ether solvents or alcohol solvents, and even more preferably amine solvents and A combination of ether solvents.

Examples of the amidine solvents include 2-pyrrolidone, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-vinyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, N, N-dimethylbutyramide, 3-methoxy-N, N-dimethylpropanamide, 3- Ethoxy-N, N-dimethylpropanamide, 3-propoxy-N, N-dimethylpropanamide, 3-isopropoxy-N, N-dimethylpropanamide, 3-butoxy-N, N-dimethylpropanamide, 3-secondary butoxy-N, N-dimethylpropylamine, 3-tertiary butoxy-N, N-dimethyl Propylamine and the like.

Examples of the ester-based solvent include ethyl acetate, methyl lactate, ethyl lactate, n-propyl lactate, n-butyl lactate, isoamyl lactate, isoamyl lactate, methyl 2-hydroxyisobutyrate, 2 -Ethyl hydroxyisobutyrate, propyl 2-hydroxyisobutyrate, butyl 2-hydroxyisobutyrate, γ-butyrolactone, and the like.

Examples of the ether-based solvent include dimethyl ether, 1,2-dimethoxyethane, ethyl cellosolve, butyl cellosolve, tetrahydrofuran, 1,4-dioxane, and cyclopentylmethyl ether. .

Examples of the alcohol-based solvent include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, tertiary butanol, 2-ethylhexanol, benzyl alcohol, and 1-methyl alcohol. Alcohol solvents such as oxy-2-propanol, 1-ethoxy-2-propanol, 1-butoxy-2-propanol, and ethylene glycol.

When the amidamine-based solvent and other solvents are used in combination, the blending ratio is preferably a amine-based solvent in terms of mass ratio: another solvent = 95: 5 to 60:40, more preferably 95: 5 to 70: 30, and more preferably 90:10 to 70:30. By setting the blending ratio of the solvent to the above range, the coating properties can be improved.

The method for preparing the composition for forming a temporary adhesive layer of the present invention is arbitrary. As a preferable example of a preparation method, the method of filtering the reaction solution containing the objective polyamic acid obtained by the method demonstrated above is mentioned. At this time, the filtrate can be diluted or concentrated if necessary for the purpose of concentration adjustment and the like. By adopting this method, not only the mixing of impurities can be reduced, but also the adhesion and peelability of the temporary adhesive layer produced from the obtained composition may be deteriorated, and a composition for forming a temporary adhesive layer can also be effectively obtained. The solvent used for the dilution is not particularly limited, and specific examples thereof include the same as the specific examples of the reaction solvent of the reaction described above. The solvent used for dilution can be used individually by 1 type or in combination of 2 or more types.

The viscosity of the composition for forming a temporary adhesive layer of the present invention is appropriately set in consideration of the thickness of the temporary adhesive layer to be produced, etc. In particular, in order to obtain a film having a thickness of about 0.05 to 5 μm with good reproducibility, usually, it is 25 The temperature is about 10 to 10,000 mPa · s, and preferably about 20 to 5,000 mPa · s.

Here, the viscosity can be measured using a viscometer for measuring the viscosity of a commercially available liquid under the condition of a temperature of 25 ° C. of the composition with reference to a program described in JIS K7117-2, for example. Preferably, as the viscometer, a conical plate type (conical plate type) rotary viscometer is used, and it is preferably a viscometer of the same type, using 1˚34 '× R24 as a standard cone rotor. Measured at 25 ° C. Examples of such a rotational viscosity meter include TVE-25L manufactured by Toki Sangyo Co., Ltd.

In addition, the composition for forming a temporary adhesive layer of the present invention may contain, in addition to the components (A) to (D), a crosslinking agent and the like in order to improve, for example, film strength.

[Temporarily follows the layer]
After the composition for forming the temporary adhesive layer described above is applied to a substrate, a firing method including a step of firing at 180 to 250 ° C. is usually used to obtain excellent adhesion to the substrate and a resin substrate. Temporary adhesive layer with moderate adhesiveness and excellent heat resistance.

The heating time varies with the heating temperature and cannot be generalized, but it is usually 1 minute to 5 hours. The temperature during the firing may include a step of firing at a temperature lower than the maximum temperature as long as the maximum temperature is within the above range.

As a preferable example of the heating state in the present invention, a state in which heating is performed at 50 to 150 ° C. for 1 minute to 1 hour, and the heating temperature is directly increased, and heating is performed at 180 to 250 ° C. for 5 minutes to 4 hours. Particularly, as a more preferable example of the heating state, a state of heating at 50 to 150 ° C for 1 minute to 1 hour, and heating at 200 to 250 ° C for 5 minutes to 2 hours can be mentioned. In addition, as another example of the heating state, a state where heating is performed at 50 to 150 ° C for 1 minute to 2 hours, and then heating is performed at 200 ° C to 250 ° C for 5 minutes to 1 hour.

When the temporary adhesive layer of the present invention is formed on a substrate, the temporary adhesive layer may be formed on a part of the surface of the substrate or may be formed on the entire surface. The temporary bonding layer is formed on a part of the surface of the substrate. The temporary bonding layer is formed only in a predetermined range on the surface of the substrate. The temporary bonding layer is formed into a dot pattern, a line, and a gap on the entire surface of the substrate. The shape of a pattern, etc. In addition, in the present invention, the base system refers to a manufacturer who can apply the composition for forming a temporary adhesive layer of the present invention on a surface thereof and can use the composition for a flexible electronic device or the like.

Examples of the substrate (base material) include glass, plastic (polycarbonate, polymethacrylate, polystyrene, polyester, polyolefin, epoxy, melamine, cellulose triacetate, ABS, AS, Pinene-based resins, etc.), metals (silicon wafers, etc.), wood, paper, slate, etc., are particularly preferred because the temporary adhesive layer of the present invention has sufficient adhesion to them. In addition, the surface of the substrate can be composed of a single material or two or more materials. As a state in which the substrate surface is composed of two or more materials, a certain range of the substrate surface is composed of a certain material, and the rest of the surface is composed of other materials. A certain material is dotted on the entire substrate surface. Pattern shapes such as patterns, line and gap patterns exist in other materials.

The method for applying the composition for forming a temporary adhesive layer of the present invention to a substrate is not particularly limited, and examples thereof include a casting coating method, a spin coating method, a doctor blade coating method, a dip coating method, a roll coating method, Rod coating method, die coating method, inkjet method, printing method (relief, gravure, lithography, screen printing, etc.) and the like.

Examples of the appliance used for heating include a hot plate and an oven. The heating environment can be under air or under an inert gas; it can also be under normal pressure or under reduced pressure.

The thickness of the temporary adhesion layer is usually about 0.01 to 50 μm, and preferably about 0.05 to 20 μm from the viewpoint of productivity. In addition, the desired thickness can be achieved by adjusting the thickness of the coating film before heating.

The glass transition temperature Tg of the temporary adhesive layer is preferably less than 300 ° C, and more preferably 260 ° C or less. The glass transition temperature Tg is less than 300 ° C. and can be fired at a lower temperature.

The temporary bonding layer of the present invention has excellent adhesion to a substrate, particularly a glass substrate, moderate adhesion to a resin substrate, moderate peelability, and excellent heat resistance, and has a small peeling force before and after the manufacturing process of an electronic device. , Can show stable adhesion. Therefore, the temporary bonding layer of the present invention can be applied to a person who peels the resin substrate together with a circuit formed on the resin substrate from the substrate without damaging the resin substrate of the device in the process of manufacturing a flexible electronic device.

[Manufacturing method of resin substrate]
Hereinafter, an example of a method for manufacturing a flexible electronic device using the temporary bonding layer of the present invention will be described. First, using the composition for forming a temporary adhesive layer of the present invention, a temporary adhesive layer is formed on a glass substrate according to the method described above. On this temporary adhesive layer, a resin substrate forming solution for forming a resin substrate is applied, and the coating film is fired to form a resin substrate fixed to a glass substrate via the temporary adhesive layer of the present invention.

The firing temperature of the coating film can be appropriately set according to the type of resin, etc. In the present invention, it is preferable to set the highest temperature during firing to 200 to 250 ° C, more preferably 210 to 250 ° C, and even more preferably It is set to 220 to 240 ° C. By setting the maximum temperature during firing of the resin substrate to this range, it is possible to further improve the adhesion between the temporary adhesion layer of the base and the substrate, and the moderate adhesion and peelability of the temporary adhesion layer and the resin substrate. In this case, as long as the maximum temperature is in the above range, a step of firing at a temperature lower than this may be included.

The resin substrate can form the resin substrate with a larger area than the area of the temporary adhesive layer by covering the entire temporary adhesive layer, or can form the resin substrate with an area smaller than the area where the temporary adhesive layer is formed. Examples of such a resin substrate include a resin substrate made of an acrylic polymer or a resin substrate made of a cyclic olefin polymer. For example, a wholly aromatic polyimide, polybenzoxazole, or polybenzothiazole is used. And resin substrates of wholly aromatic polymers such as polybenzimidazole. A mixed film in which silica sol, titanium dioxide sol, or the like is added to the polymer may be used. In addition, the temporary adhesive layer of the present invention can be more suitably used among the above-mentioned various substrates, especially when a resin substrate that does not exhibit adhesion to a glass substrate is used. As such a resin substrate, for example, polyfluorene containing fluorine atoms can be exemplified. Resin substrate made of imine. The method for forming the above-mentioned resin substrate may be a conventional method. Moreover, as for the said resin substrate, it is preferable that the light transmittance of a wavelength of 450 nm is 80% or more.

Next, a desired circuit is formed on the resin substrate fixed to the substrate via the temporary bonding layer of the present invention, and thereafter, the resin substrate is cut into a predetermined shape together with, for example, the temporary bonding layer, and the resin substrate is temporarily changed with the circuit. Then, the layer was peeled off to separate the resin substrate from the substrate. At this time, a part of the substrate may be cut together with the temporary bonding layer.

The peeling force from the substrate is higher than the peeling force from the resin substrate, and the peeling force from the resin substrate is 0.1 to 0.3 N / 25 mm, preferably 0.15 to 0.3 N / 25 mm before the electronic device is manufactured. After the electronic device is manufactured, the electronic device is 0.1 to 0.3 N / 25 mm, preferably 0.15 to 0.3 N / 25 mm, and more preferably 0.2 to 0.3 N / 25 mm. If the peeling force after the electronic device is manufactured is too large compared to the peeling force before the electronic device is manufactured, the resin substrate cannot be peeled off eventually; if it is too small, the resin substrate cannot be stably fixed on the substrate, and there is no stability. Carry out the electronic device manufacturing.

In addition, the change in the peeling force after the electronic device is manufactured is preferably less than ± 0.1N / 25mm, and more preferably less than ± 0.1N / 25mm, compared to the peeling force before the electronic device is manufactured, from the viewpoint of stably fixing the resin substrate. 0.05N / 25mm.

In addition, the term "after manufacture of an electronic device" as used in the present invention refers to the meaning after implementing the manufacturing steps (processes) of an electronic device composed of the following steps (1) to (3). According to the present invention, even after going through these steps, the change in the adhesive force of the temporary adhesive layer to the resin substrate is small, and the resin substrate can be stably fixed.
(1) A step of immersing the substrate on which the temporary bonding layer and the resin substrate are formed in a 3% potassium hydroxide aqueous solution for 5 minutes, and heating at 250 ° C for 50 minutes.
(2) Next, the substrate is immersed in a predetermined ITO etching material for 5 minutes, and then heated at 250 ° C for 50 minutes.
(3) A step of further immersing in the ITO etching material for 5 minutes and heating at 250 ° C for 50 minutes

The ITO etching material is generally a mixed aqueous solution of 30% iron (III) chloride aqueous solution and 12% hydrogen chloride water, but commercially available products can be used, and examples thereof include PE-560 (manufactured by Ching Young Industrial Co., Ltd.) .

[Example]

Examples are given below to explain the present invention in more detail, but the present invention is not limited to these examples.

[1] Abbreviation for compound
p-PDA: p-phenylenediamine
ODA: 4.4-diaminodiphenyl ether
TFMB: 2,2'-trifluoromethylbenzidine
BPDA: 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride
TAHQ: p-phenylene bis (trimellitic acid monoester anhydride)
6FDA: 4,4 '-(hexafluoroisopropylidene) diphthalic anhydride
NMP: N-methyl-2-pyrrolidone
BCS: Butyl Cellosolve
DMAc: N, N'-dimethylacetamide
APTMS: 3-aminopropyltrimethoxysilane

[2] Measurement of weight-average molecular weight and molecular weight distribution The measurement of the weight-average molecular weight of the polymer (hereinafter referred to as Mw) and the measurement of the molecular weight distribution was performed using a GPC device (column: KD801 and KD805 manufactured by Shodex) made in The elution solvent was dimethylformamide / LiBr · H ₂ O (29.6mM) / H ₃ PO ₄ (29.6mM) / THF (0.1wt%), the flow rate was 1.0mL / min, and the column temperature was 40 ° C. Perform the measurement. In addition, Mw is a standard polystyrene conversion value.

[3] Measuring device for glass transition temperature Tg: DMA Q-800 manufactured by TA Instruments
Heating rate: 10 ℃ / min Measuring temperature: 25 ～ 400 ℃

[4] Synthesis of polymer A polyamino acid was synthesized according to the following method.
In addition, the polymer was not separated from the reaction liquid containing the obtained polymer, but as described later, the reaction liquid was diluted to prepare a composition for forming a resin substrate or a composition for temporarily adhering a layer.

<Synthesis of Synthesis Example S1 Polyamine (S1)>
TFMB9.496g (0.02965 mol) was dissolved in DMAc113.3g, BPDA 5.234g (0.01779 mol) and 6FDA 5.269g (0.01186 mol) were added, and then reacted at 23 ° C. for 24 hours under a nitrogen atmosphere. The obtained polymer had a Mw of 37,300 and a molecular weight distribution of 2.6.

<Synthesis of Synthesis Example L1 Polyamic Acid (L1)>
0.931 g (0.00861 mol) of p-PDA was dissolved in 35.2 g of NMP. TAHQ3.868g (0.00845 mol) was added to the obtained solution, and it was made to react at 23 degreeC for 24 hours in nitrogen atmosphere. Mw was 45,000 and Mw / Mn was 2.7.

<Synthesis of Synthesis Example L2 Polyamic Acid (L2)>
1.65 g (0.00983 mol) of ODA was dissolved in 35.2 g of NMP. To the obtained solution, 2.834 g (0.00963 mol) of BPDA was added, and the mixture was reacted at 23 ° C. for 24 hours under a nitrogen atmosphere. Mw was 35,000 and Mw / Mn was 2.9.

<Synthesis of Synthesis Example L3 Polyamic Acid (L3)>
TFMB 1.965 g (0.00650 moles) was dissolved in NMP 35.2 g. To the obtained solution were added TAHQ 0.298 g (0.00065 mol) and BPDA 1.720 g (0.00585 mol), and the mixture was reacted at 23 ° C. for 24 hours under a nitrogen atmosphere. Mw was 45,000 and Mw / Mn was 3.9.

[5] Preparation of a composition (varnish) for temporarily adhering a layer
[Example 1-1]
In an eggplant-shaped flask, 3 g of polyamino acid L1 and 7 g of polyamino acid L2 were stirred at 23 ° C. for 3 hours. Thereafter, 1.2 g of an NMP solution diluted to 1% APTMS was added dropwise, further NMP 8.43 g and BCS 4.6 g were added dropwise, and the mixture was further stirred for 24 hours to obtain a composition A for temporarily forming a layer.

[Example 1-2]
A composition B for temporary adhesion layer formation was obtained in the same manner as in Example 1-1, except that the NMP solution diluted to 2% APTMS was used instead of the NMP solution diluted to 1% APTMS.

[Example 1-3]
A composition for temporary bonding layer formation was obtained in the same manner as in Example 1-1, except that polyglycine L1 3g and polyglycine L2 7g were changed to polyglycine L1 2g and polyglycine L2 8g.物 C。 C.

[Comparative Example 1-1]
In an eggplant-shaped flask, 3 g of polyamino acid L1 and 7 g of polyamino acid L2 were stirred at 23 ° C. for 3 hours. Thereafter, 9.63 g of NMP and 4.6 g of BCS were added dropwise, and the mixture was further stirred for 24 hours to obtain composition a for temporarily forming a layer.

[Comparative Example 1-2]
A composition b for forming a temporary adhesive layer was obtained in the same manner as in Comparative Example 1-1, except that 0.12 g of Primid XL552 (manufactured by Dainippon Paint Co., Ltd.) was added.

[Comparative Example 1-3]
Except adding 10 g of polyamic acid L3, 0.12 g of Celloxide 2021P (manufactured by DAICEL Chemical Co., Ltd.) to eggplant-type flasks in place of 3 g of polyamino acid L and 7 g of polyamino acid L2, it was the same as Comparative Example 1- 1 In the same manner, a composition c for temporarily forming a layer was obtained.

[Comparative Example 1-4]
In an eggplant-type flask, 10 g of polyamidic acid L2 was stirred at 23 ° C for 3 hours. Thereafter, 1.2 g of a NMP solution diluted to 5% of APTES was added dropwise, and then NMP 8.43 g and BCS 4.6 g were added dropwise, and the mixture was further stirred for 24 hours to obtain a composition d for temporarily forming a layer.

[6] Measurement of the glass transition temperature Tg of the temporary adhesive layer The Tg of the temporary adhesive layer obtained by curing the composition for forming a temporary adhesive layer is measured according to the following procedure.
Using a bar coater (gap: 250 μm), the composition for forming a temporary adhesive layer obtained in Examples 1-1 to 1-3, Comparative Examples 1-1, and 1-4 was applied to 100 mm of a glass substrate. × 100mm glass substrate. Then, the obtained coating film was heated at 120 ° C. for 3 minutes using a hot plate, and then heated at 240 ° C. for 60 minutes using an oven to form a thin film (temporary adhesive layer) having a thickness of about 6 μm on a glass substrate to obtain a thin film Glass substrate. Thereafter, the obtained glass substrate with a film was immersed in pure water filled in a 2 L beaker, and the film was peeled from the glass substrate. Then, a 5 mm × 70 mm test piece was prepared from the obtained film, and Tg was measured by DMA. The results are shown in Table 1.

[7] Formation of temporary bonding layer and resin substrate
[Example 2-1]
Using a spin coater (condition: 3,000 rpm, about 30 seconds), the composition A for temporary bonding layer formation obtained in Example 1-1 was applied to a 100 mm × 100 mm glass substrate (the same applies hereinafter). )on.
Then, the obtained coating film was heated at 120 ° C. for 3 minutes using a hot plate, and then heated at 240 ° C. for 60 minutes using an oven to form a temporary adhesive layer having a thickness of about 0.1 μm on a glass substrate to obtain a temporary adhesive layer. Glass substrate. In addition, during the temperature rise period, the glass substrate was not taken out of the oven, but was heated in the oven.

Next, using a bar coater (gap: 250 μm), the composition S1 for forming a resin substrate was coated on the temporary adhesion layer (resin film) on the glass substrate with the temporary adhesion layer obtained above. Then, the obtained coating film was heated at 150 ° C. for 10 minutes using a hot plate, and then heated at 250 ° C. for 60 minutes using an oven to form a resin substrate having a thickness of about 10 μm on the temporary adhesive layer to obtain a resin substrate. A layer of glass substrate. In addition, as a result of measuring the light transmittance using an ultraviolet-visible spectrophotometer (UV-2600, manufactured by Shimadzu Corporation), the resin substrate showed a transmittance of 95% or more at 450 nm.

[Examples 2-2 to 2-3]
Except that the temporary adhesive layer formation compositions B and C obtained in Examples 1-2 to 1-3 were used instead of the temporary adhesive layer formation composition A obtained in Example 1-1, they are the same as in the examples. 2-1 A temporary bonding layer and a resin substrate were formed in the same manner, and a glass substrate with a temporary bonding layer and a glass substrate with a resin substrate and a temporary bonding layer were obtained.

[Comparative Examples 2-1 to 2-4]
Except that the temporary adhesive layer formation compositions a to d obtained in Comparative Examples 1-1 to 1-4 were used in place of the temporary adhesive layer formation composition A obtained in Example 1-1, respectively, it is the same as in the examples. 2-1 A temporary bonding layer and a resin substrate were formed in the same manner, and a glass substrate with a temporary bonding layer and a glass substrate with a resin substrate and a temporary bonding layer were obtained.

[Comparative Example 2-5]
A resin substrate was formed in the same manner as in Example 2-1 except that a temporary adhesive layer was not formed on the glass substrate, and a glass substrate with a resin substrate was obtained.

[8] Evaluation of peelability (temporary adhesion)
[Examples 2-1 to 2-3, Comparative Examples 2-1 to 2-5]
Regarding the glass substrate with a temporary adhesive layer obtained in the above Examples 2-1 to 2-3 and Comparative Examples 2-1 to 2-4, the peelability between the temporary adhesive layer and the glass substrate was confirmed by the following method, and For a glass substrate with a resin substrate and a temporary adhesive layer, confirm the peeling force and step stability of the temporary adhesive layer and the resin substrate in the following manner. In addition, the resin substrate of the glass substrate with a resin substrate obtained in Comparative Example 2-5 was also evaluated similarly for items that could be evaluated.

＜ Evaluation of peelability of temporary adhesion layer and glass substrate ＞
The temporary bonding layer on the glass substrate with the temporary bonding layer obtained in Examples 2-1 to 2-3 and Comparative Examples 2-1 to 2-4 was cross-cut (a 2 mm vertical and horizontal interval, the same applies hereinafter), and Cut into 25 squares. That is, 25 cross-cut squares are formed by this cross cutting.
Thereafter, the tape was cut into 25 sections, and the tape was peeled off. The peelability was evaluated based on the following criteria. The results are shown in Table 1.

<Judgment criteria>
5B: 0% peeling (no peeling)
4B: Less than 5% peeling
3B: 5 to less than 15% peeling
2B: 15 to less than 35% peeling
1B: 35 to 65% peeling
0B: 65% to 80% peeling
B: 80% to less than 95% peeling
A: 95% to 100% peeling
AA: 100% peeling (full peeling)

＜ Evaluation of peeling force between temporary adhesive layer and resin substrate ＞
Using a cutter, the resin substrate with the resin substrate and the glass substrate temporarily bonded to the layer obtained in Examples 2-1 to 2-3 and Comparative Examples 2-1 to 2-4, and the resin substrate obtained in Comparative Example 2-5 were used. The resin substrate of the glass substrate with the resin substrate was cut into a strip shape of 25 mm × 50 mm. Then, a transparent tape (NICHIBAN CT-24) was stuck to the front end of the cut resin substrate, and this was used as a test piece. This test piece was subjected to a peel test using Autograph AG-500N (manufactured by Shimadzu Corporation) at a peel angle of 90 degrees, and the peel force was measured. In addition, those who cannot be separated are rated as "unable to be separated". The results are shown in Table 1.

＜ Step stability ＞
Resin substrate-attached glass substrates obtained in Examples 2-1 to 2-3 and Comparative Examples 2-1 to 2-4 and glass substrates with resin substrates obtained in Comparative Examples 2-5 The substrate is subjected to a process consisting of the following steps (1) to (3), and the state of the resin substrate after the implementation is evaluated according to the following criteria. The results are shown in Table 1.
(1) After being immersed in a 3% potassium hydroxide aqueous solution for 5 minutes, it was heated at 250 ° C for 50 minutes.
(2) After immersion in ITO etching material PE-560 (manufactured by Elite Industries Co., Ltd.) for 5 minutes, heating was performed at 250 ° C for 50 minutes.
(3) After being immersed in the ITO etching material again for 5 minutes, it was heated at 250 ° C for 50 minutes.

[Judgment criteria]
○: No change △: Partial peeling ×: Whole surface peeling

<Change in peeling force of temporarily adhered layer>
Confirm the resin substrate-attached glass substrate obtained in Examples 2-1 to 2-3, Comparative Examples 2-1 to 2-4, and the glass substrate with resin substrate obtained in Comparative Example 2-5. After the step of the resin substrate of the substrate was stabilized, the resin substrate was cut into 25 mm × 50 mm short strips using a dicing blade. Then, a transparent tape was stuck to the tip of the cut resin substrate, and this was used as a test piece. For this test piece, a peeling test was performed using Autograph AG-500N so that the peeling angle was 90 degrees, and the peeling force was measured and compared with the peeling force before the implementation of the process.
Changes in the peeling force before and after the implementation of the process were evaluated according to the following criteria. In addition, those who cannot be separated are rated as "unable to be separated". The results are shown in Table 1.

[Judgment criteria]
◎: The change of peeling force is less than ± 0.05N / 25mm, and the peeling force before and after the implementation of the process is in the range of 0.2 to 0.3N / 25mm. 0.1N / 25mm, and the peeling force before and after the implementation of the process is in the range of 0.2 to 0.3N / 25mm △: The change of the peeling force is ± 0.1N / 25mm or more, and the peeling force before and after the implementation of the process is 0.1 to In the range of 0.3N / 25mm □: The change in peeling force is ± 0.1N / 25mm or more, and at least one of the peeling force before and after the process is implemented is outside the range of 0.1 to 0.3N / 25mm ×: Occurs during the process Peeling and cannot be measured
-: Not peeled at all.

As shown in Table 1, the temporary adhesive layers obtained in the examples were confirmed to have excellent adhesion to the substrate, moderate adhesion to the resin substrate, and appropriate peelability, and the peel force before and after the manufacturing process of the electronic device The change is small, and the step stability is excellent.
On the other hand, in the case of the comparative example, it was confirmed that the resin substrate was peeled during the implementation of the process, and the step stability was poor (Comparative Example 2-1); the resin substrate could not be peeled from the beginning (Comparative Examples 2-2, 2 -3); Although the step stability is good, the large peeling force varies greatly and eventually cannot be peeled off (Comparative Example 2-4). In addition, in Comparative Example 2-5 in which a temporary adhesive layer was not formed, and the same resin substrate as the resin substrate formed in the example was directly formed on the substrate, it was confirmed that the resin substrate could not be stably fixed to the substrate, and the step stability was poor. .

Claims (13)

A composition for temporarily bonding layers is used for forming an electronic device on a resin substrate laminated on the surface of a substrate. The composition is interposed between the substrate and the resin substrate to form and fix the resin substrate to the substrate. The composition of the temporary adhesion layer on the surface is characterized by comprising: (A) a polyamic acid represented by the following formula (P1), (B) a polyamino acid represented by the following formula (P2), (C) a silane coupling agent having an amine group or a urea group, and (D) a mixed solvent containing two or more kinds selected from the group consisting of a fluorene-based solvent, an ester-based solvent, an ether-based solvent, and an alcohol-based solvent, and provides: The peeling force of the substrate is higher than the peeling force from the resin substrate, and the peeling force from the resin substrate is 0.1 to 0.3 N / 25 mm before the electronic device is manufactured, and 0.1 to 0.3 after the electronic device is manufactured. N / 25mm temporary bonding layer; (In the formula, X ¹ represents a divalent aromatic group having two carboxyl groups and an ester bond, or a divalent aromatic group having two carboxyl groups and no ester bond; Y ¹ represents a divalent aromatic group having an ester bond. Or a divalent aromatic group without an ester bond, at least one of X ¹ and Y ¹ is an aromatic group with an ester bond, and m represents a natural number) (In the formula, X ² represents a divalent aromatic group having two carboxyl groups and an ether bond, or a divalent aromatic group having two carboxyl groups and no ether bond; Y ² represents a divalent aromatic group having an ether bond. Or a divalent aromatic group having no ether bond, at least one of X ² and Y ² is an aromatic group having an ether bond, and n represents a natural number). For example, the composition for forming a temporary adhesive layer of claim 1, wherein X ¹ is an aromatic group represented by the following formula (1) or (2): . For example, the composition for temporary layer formation of claim 1 or 2, wherein X ² is an aromatic group represented by the following formula (3): . The composition for temporarily forming a layer according to any one of claims 1 to 3, wherein Y ¹ is an aromatic group represented by any one of the following formulae (4) to (6): . The composition for temporarily forming a layer according to any one of claims 1 to 4, wherein Y ² is an aromatic group represented by the following formula (7) or (8): . The temporary adhesive layer-forming composition according to any one of claims 1 to 5, wherein either or both of the component (A) and the component (B) are polyamic acid having an amine group at both ends. In the composition for forming a temporary adhesive layer according to any one of claims 1 to 6, wherein the blending mass ratio of the component (A) to the component (B) is (A): (B) = 2: 8 to 8: 2. The composition for forming a temporary adhesive layer according to any one of claims 1 to 7, wherein the component (C) is aminopropyltrimethoxysilane, and its content is relative to the total of the components (A) and (B) The mass is less than 5 mass%. The temporary adhesive layer-forming composition according to any one of claims 1 to 8, wherein the component (D) is a mixed solvent containing one or more organic solvents selected from the amidine-based solvents. A temporary adhesive layer formed by using the composition for forming a temporary adhesive layer according to any one of claims 1 to 9. If the temporary adhesive layer of claim 10 is used, its glass transition temperature is less than 300 ° C. A laminated body formed by forming a resin layer having a light transmittance of 450% or more at a wavelength of 450 nm on a temporary adhesive layer as in claim 10 or 11. An electronic device manufacturing method includes: A step of applying the composition for forming a temporary adhesive layer according to any one of claims 1 to 9 on a substrate to form a temporary adhesive layer; A step of forming a resin substrate having a light transmittance of more than 80% at a wavelength of 450 nm on the temporary adhesive layer; A step of fabricating an electronic device on the resin substrate; and A step of peeling the resin substrate with a peeling force of 0.1 to 0.3 N / 25 mm.