JPWO2016158990A1 - Release layer forming composition and release layer - Google Patents

Abstract

Provided is a composition for forming a release layer comprising a polyamic acid obtained by introducing an anchor group at one or both of the polymer chain ends and an organic solvent.

Description

  The present invention relates to a release layer forming composition and a release layer.

  In recent years, electronic devices have been required to have the functions of bending, thinning and lightening. For this reason, it is required to use a lightweight flexible plastic substrate in place of the conventional glass substrate that is fragile and cannot be bent. In the new generation display, development of an active full-color TFT display panel using a lightweight flexible plastic substrate is required.

  Therefore, various methods for manufacturing electronic devices using a resin film as a substrate are being studied, and in the new generation display, manufacturing studies are being carried out in a process that can divert existing TFT equipment. In Patent Documents 1, 2, and 3, an amorphous silicon thin film layer is formed on a glass substrate, a plastic substrate is formed on the thin film layer, and then a laser is irradiated from the glass surface side to accompany crystallization of amorphous silicon. A method of peeling a plastic substrate from a glass substrate with generated hydrogen gas is disclosed.

  Patent Document 4 discloses a method for attaching a layer to be peeled (described as “transfer target layer” in Patent Document 4) to a plastic film by using the techniques disclosed in Patent Documents 1 to 3 to complete a liquid crystal display device. Is disclosed.

  However, in the methods disclosed in Patent Documents 1 to 4, particularly the method disclosed in Patent Document 4, it is essential to use a substrate having high translucency, and hydrogen contained in amorphous silicon is allowed to pass through the substrate. In order to give sufficient energy for the emission, it is necessary to irradiate a laser beam having a relatively large energy, and there is a problem that the layer to be peeled is damaged. In addition, since it takes a long time for the laser treatment and it is difficult to peel off the peeled layer having a large area, there is a problem that it is difficult to increase the productivity of device fabrication.

Japanese Patent Laid-Open No. 10-125929 Japanese Patent Laid-Open No. 10-125931 International Publication No. 2005/050754 Japanese Patent Laid-Open No. 10-125930

  This invention is made | formed in view of the said situation, The composition for peeling layer formation for forming the peeling layer which can peel without damaging the resin substrate of a flexible electronic device, and the said peeling layer are provided. The purpose is to provide.

  As a result of intensive studies to solve the above problems, the present inventors have obtained a composition comprising a polyamic acid obtained by introducing an anchor group at either or both of the polymer chain ends, and an organic solvent. The present inventors have found that a release layer having an excellent adhesion to a substrate and an appropriate adhesion to a resin substrate used in a flexible electronic device and an appropriate peelability can be formed.

That is, the present invention
1. A composition for forming a release layer, comprising a polyamic acid obtained by introducing an anchor group into either one or both of the polymer chain ends, and an organic solvent,
2. 1. The composition for forming a release layer, wherein the anchor group is a silyl group or a carboxylic acid group,
3. 1 or 2 peeling, wherein the polyamic acid is a polyamic acid obtained by reacting a diamine component containing an aromatic diamine and an acid dianhydride component containing an aromatic tetracarboxylic dianhydride Layer forming composition,
4). 3. The composition for forming a release layer according to 3, wherein the aromatic diamine is an aromatic diamine containing 1 to 5 benzene nuclei,
5. The composition for forming a release layer according to 3 or 4, wherein the aromatic tetracarboxylic dianhydride is an aromatic tetracarboxylic dianhydride containing 1 to 5 benzene nuclei,
6). A release layer formed using the release layer forming composition according to any one of 1 to 5,
7). A method for producing a flexible electronic device comprising a resin substrate, characterized in that a release layer of 6 is used,
8). The manufacturing method according to 7 is characterized in that the resin substrate is a substrate made of polyimide.

  By using the composition for forming a release layer of the present invention, it is possible to obtain a release layer having excellent adhesion to a substrate, moderate adhesion to a resin substrate, and moderate release with good reproducibility. Therefore, by using the composition for forming a release layer of the present invention, in the manufacturing process of the flexible electronic device, without damaging the resin substrate formed on the substrate, the circuit provided on the substrate, and the like. The resin substrate can be separated from the substrate together with the circuit and the like. Therefore, the composition for forming a release layer of the present invention can contribute to simplification of the production process of a flexible electronic device including a resin substrate, improvement of its yield, and the like.

Hereinafter, the present invention will be described in more detail.
The composition for forming a release layer of the present invention contains a polyamic acid obtained by introducing an anchor group at one or both of the polymer chain ends, and an organic solvent. Here, the release layer in the present invention is a layer provided immediately above a glass substrate for a predetermined purpose. As a typical example, in a manufacturing process of a flexible electronic device, a flexible electronic made of a substrate and a resin such as polyimide is used. Provided between the device resin substrate and the resin substrate in a predetermined process, and after the electronic circuit or the like is formed on the resin substrate, the resin substrate can be easily peeled from the substrate. For example, a release layer may be used.

  The polyamic acid used in the present invention is not particularly limited as long as it has an anchor group at the end of the polymer chain, but the polyamic acid obtained after reacting the diamine component with the tetracarboxylic dianhydride component And an amine having an anchor group or an acid anhydride having an anchor group can be obtained. That is, the polyamic acid obtained here is one in which either or both of the molecular chain ends are sealed with an anchor group-containing compound described later.

  Examples of such anchor groups include carboxylic acid groups, silyl groups (for example, alkylsilyl groups, alkoxysilyl groups, vinylsilyl groups, and allylsilyl groups), vinyl groups, maleimide groups, phenolic hydroxyl groups, and the like. Carboxylic acid groups and silyl groups (particularly silyl groups in which one or more groups selected from alkoxy groups, vinyl groups and allyl groups are bonded to silicon atoms) are preferred. By using such an anchor group, the skeleton can be different from the flexible substrate used for the upper layer, so that the function of the obtained film as a release layer can be improved.

In the present invention, the anchor group may be present at either one of the polymer chain ends of the polyamic acid, but it is preferable that the anchor group be present at both of the polymer chain ends.
Moreover, between the polyamic acid obtained from a diamine component and a tetracarboxylic dianhydride component, and an anchor group, the C1-C10 alkyl group and aryl which do not reduce remarkably and heat resistance remarkably A spacer group such as a group may be present, and an ether bond, a thioether bond, an ester bond or the like may be present in these spacer groups.

  Specific examples of the amine having an anchor group include 4-aminophenoxytrimethylsilane, 4-aminophenoxydimethylvinylsilane, 4-aminophenoxymethyldivinylsilane, 4-aminophenoxytrivinylsilane, 4-aminophenoxydimethylallylsilane, 4-amino. Phenoxymethyldiallylsilane, 4-aminophenoxytriallylsilane, 4-aminophenoxydimethylphenylsilane, 4-aminophenoxymethyldiphenylsilane, 4-aminophenoxytriphenylsilane, 4-aminophenoxytrimethoxysilane, 4-aminophenoxydimethoxyvinylsilane 4-aminophenoxymethoxydivinylsilane, 4-aminophenoxytrivinylsilane, 4-aminophenoxydimethoxyallylsilane, 4- Minophenoxymethoxydiallylsilane, 4-aminophenoxydimethoxyphenylsilane, 4-aminophenoxymethoxydiphenylsilane, 4-aminophenoxytriethoxysilane, 4-aminophenoxydiethoxyvinylsilane, 4-aminophenoxyethoxydivinylsilane, 4-aminophenoxy Trivinylsilane, 4-aminophenoxydiethoxyallylsilane, 4-aminophenoxyethoxydiallylsilane, 4-aminophenoxydiethoxyphenylsilane, 4-aminophenoxyethoxydiphenylsilane, 3-aminophenoxytrimethylsilane, 3-aminophenoxydimethylvinylsilane, 3-aminophenoxymethyldivinylsilane, 2-aminophenoxytrivinylsilane, 2-aminophenoxytrimethyl Silane, 2-aminophenoxydimethylvinylsilane, 2-aminophenoxymethyldivinylsilane, 2-aminophenoxytrivinylsilane, 3-aminopropyltriethylsilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-amino Propyltrimethoxysilane, 2-aminopropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N-ethoxy Carbonyl-3-aminopropyltrimethoxysilane, N-ethoxycarbonyl-3-aminopropyltriethoxysilane, N-triethoxysilylpropyltriethylenetriamine, N-trimethoxysilylpropyltriethyl Examples include, but are not limited to, lentriamine, 2-aminophenol, 3-aminofail, 4-aminophenol, and the like.

  Specific examples of the acid anhydride having an anchor group include trimellitic anhydride, vinylmaleic anhydride, 4-vinylnaphthalene-1,2-dicarboxylic anhydride, maleic anhydride, and 2,3-dimethylmaleic acid. Examples thereof include, but are not limited to, anhydrides, 4-hydroxyphthalic anhydride, 3-hydroxyphthalic anhydride, and the like.

  Moreover, as a diamine component and an acid dianhydride component used when producing a polyamic acid, from the viewpoint of improving the function as a release layer of the obtained film, a diamine component containing an aromatic diamine and an aromatic tetracarboxylic acid dicarboxylic acid are used. A polyamic acid obtained by reacting an acid dianhydride component containing an anhydride is preferred.

The aromatic diamine is not particularly limited as long as it has two amino groups in the molecule and has an aromatic ring, but an aromatic diamine containing 1 to 5 benzene nuclei is preferable.
Specific examples thereof include 1,4-diaminobenzene (p-phenylenediamine), 1,3-diaminobenzene (m-phenylenediamine), 1,2-diaminobenzene (o-phenylenediamine), and 2,4-diamino. Toluene, 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-phenylenediamine, m-xylylenediamine, p-xylylenediamine, 5-trifluoromethylbenzene-1 , 3-diamine, 5-trifluoromethylbenzene-1,2-diamine, 3,5-bis (trifluoromethyl A diamine having a single benzene nucleus such as benzene-1,2-diamine; 1,2-naphthalenediamine, 1,3-naphthalenediamine, 1,4-naphthalenediamine, 1,5-naphthalenediamine, 1,6-naphthalenediamine 1,7-naphthalenediamine, 1,8-naphthalenediamine, 2,3-naphthalenediamine, 2,6-naphthalenediamine, 4,4′-biphenyldiamine, 2,2′-bis (trifluoromethyl) -4 , 4′-diaminobiphenyl, 3,3′-dimethyl-4,4′-diaminodiphenylmethane, 3,3′-dicarboxy-4,4′-diaminodiphenylmethane, 3,3 ′, 5,5′-tetramethyl -4,4'-diaminodiphenylmethane, 4,4'-diaminobenzanilide, 3,3'-dichlorobenzidine, 3,3'-dimethylbenz 2,2'-dimethylbenzidine, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 2,2-bis (3-aminophenyl) propane, 2,2 -Bis (4-aminophenyl) propane, 2,2-bis (3-aminophenyl) -1,1,1,3,3,3-hexafluoropropane, 2,2-bis (4-aminophenyl)- 1,1,1,3,3,3-hexafluoropropane, 3,3′-diaminodiphenyl sulfoxide, 3,4′-diaminodiphenyl sulfoxide, 4,4′-diaminodiphenyl sulfoxide, 3,3′-bis ( Trifluoromethyl) biphenyl-4,4′-diamine, 3,3 ′, 5,5′-tetrafluorobiphenyl-4,4′-diamine, 4,4′-diaminoocta Benzene nuclei such as luorobiphenyl, 2- (3-aminophenyl) -5-aminobenzimidazole, 2- (4-aminophenyl) -5-aminobenzoxazole and the like are diamines; 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-aminophenyl sulfide) benzene, 1,3-bis (4-aminophenyl sulfide) benze 1,4-bis (4-aminophenylsulfide) benzene, 1,3-bis (3-aminophenylsulfone) benzene, 1,3-bis (4-aminophenylsulfone) benzene, 1,4-bis (4 -Aminophenylsulfone) benzene, 1,3-bis [2- (4-aminophenyl) isopropyl] benzene, 1,4-bis [2- (3-aminophenyl) isopropyl] benzene, 1,4-bis [2 -(4-Aminophenyl) isopropyl] benzene, 4,4 ″ -diamino-p-terphenyl, 4,4 ″ -diamino-m-terphenyl and the like, and diamine having three diamines. However, it is not limited to these. These can be used alone or in combination of two or more. In the present invention, the aromatic diamine preferably does not contain an ether bond or an ester bond.

  Among them, from the viewpoint of improving the function of the resulting film as a release layer, an aromatic ring and an aromatic ring composed only of an aromatic ring having no substituent such as a methyl group and a heteroaromatic ring on the heterocyclic ring condensed thereto. Group diamines are preferred. Specifically, p-phenylenediamine, m-phenylenediamine, 2- (3-aminophenyl) -5-aminobenzimidazole, 2- (4-aminophenyl) -5-aminobenzooxol, 4,4 ′ '-Diamino-p-terphenyl and the like are preferred.

  The aromatic tetracarboxylic dianhydride is not particularly limited as long as it has two dicarboxylic anhydride sites in the molecule and has an aromatic ring, but an aromatic carboxylic acid containing 1 to 5 benzene nuclei. Group tetracarboxylic dianhydrides are preferred.

  Specific examples thereof include pyromellitic dianhydride, benzene-1,2,3,4-tetracarboxylic dianhydride, 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'-tetra Carboxylic dianhydride, anthracene-1, , 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 dianhydride Phenanthrene-2,3,9,10-tetracarboxylic dianhydride, phenanthrene-3,4,5,6-tetracarboxylic dianhydride, phenanthrene-3,4,9,10-tetracarboxylic dianhydride However, the present invention is not limited to these. These can be used alone or in combination of two or more.

  Among these, an aromatic carboxylic dianhydride having one or two benzene nuclei is preferable from the viewpoint of improving the function of the obtained film as a release layer. Specifically, an aromatic tetracarboxylic dianhydride represented by any one of formulas (C1) to (C12) is preferable, and any one of formulas (C1) to (C7) and (C9) to (C11) The aromatic tetracarboxylic dianhydride shown is more preferred.

  In addition, from the viewpoint of improving the flexibility, heat resistance, etc. of the resulting release layer, the diamine component used in the present invention may contain a diamine other than an aromatic diamine, and the tetracarboxylic dianhydride component used in the present invention is Further, tetracarboxylic dianhydrides other than aromatic tetracarboxylic dianhydrides may be included.

  In the present invention, the amount of aromatic diamine in the diamine component is preferably 70 mol% or more, more preferably 80 mol% or more, still more preferably 90 mol% or more, still more preferably 95 mol% or more, and most preferably 100 mol%. The amount of aromatic tetracarboxylic dianhydride in the tetracarboxylic acid component is preferably 70 mol% or more, more preferably 80 mol% or more, still more preferably 90 mol% or more, and still more preferably 95 mol%. Above, most preferably 100 mol%. By adopting such a use amount, it is possible to obtain a film having excellent adhesion to the substrate, moderate adhesion to the resin substrate, and moderate peelability with good reproducibility.

  After reacting the diamine component and the tetracarboxylic dianhydride component described above, the polyamic acid obtained is reacted with an amine having an anchor group or an acid anhydride having an anchor group. A polyamic acid having an anchor group at the end of the polymer chain contained in the composition for forming a release layer can be obtained.

  The organic solvent used in such a reaction is not particularly limited as long as it does not adversely affect the reaction. Specific examples thereof include m-cresol, 2-pyrrolidone, N-methyl-2-pyrrolidone, N- Ethyl-2-pyrrolidone, N-vinyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, 3-methoxy-N, N-dimethylpropylamide, 3-ethoxy-N, N-dimethylpropyl Amide, 3-propoxy-N, N-dimethylpropylamide, 3-isopropoxy-N, N-dimethylpropylamide, 3-butoxy-N, N-dimethylpropylamide, 3-sec-butoxy-N, N-dimethyl And propylamide, 3-tert-butoxy-N, N-dimethylpropylamide, and γ-butyrolactone. . In addition, you may use an organic solvent individually by 1 type or in combination of 2 or more types.

  The charging ratio of the diamine component and the tetracarboxylic dianhydride component is appropriately determined in consideration of the target molecular weight and molecular weight distribution, the type of diamine and the type of tetracarboxylic dianhydride, etc. The diamine component is about 0.7 to 1.3, preferably about 0.8 to 1.2, and more preferably about 0.9 to 1.1 with respect to the tetracarboxylic dianhydride component 1.

  The amount of the amine having an anchor group and the acid anhydride having an anchor group is about 0.01 to 0.6, preferably 0.05 to 0, of the amine having an anchor group with respect to the tetracarboxylic dianhydride component. About 0.4, more preferably about 0.1 to 0.2, or an acid anhydride having an anchor group with respect to the diamine component of about 0.01 to 0.52, preferably about 0.05 to 0.32. Preferably it is about 0.1-0.2.

  What is necessary is just to set reaction temperature suitably in the range from melting | fusing point to the boiling point of the solvent to be used, and it is about 0-100 degreeC normally, However, Imidation in the solution of the obtained polyamic acid is prevented and high content of a polyamic acid unit is contained. In order to maintain the amount, the temperature is preferably about 0 to 70 ° C, more preferably about 0 to 60 ° C, and still more preferably about 0 to 50 ° C.

  Although the reaction time depends on the reaction temperature and the reactivity of the raw material, it cannot be defined unconditionally, but is usually about 1 to 100 hours.

  The weight average molecular weight of the polyamic acid thus obtained is usually about 5,000 to 500,000, but preferably 10,000 to 200,000 from the viewpoint of improving the function of the resulting film as a release layer. About 000, more preferably about 30,000 to 150,000. In addition, in this invention, a weight average molecular weight is a polystyrene conversion value by a gel permeation chromatography (GPC) measurement.

  The composition for forming a release layer of the present invention contains an organic solvent. As this organic solvent, the same thing as the specific example of the reaction solvent of the said reaction is mentioned. Among them, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, 1,3-dimethyl-, which dissolve polyamic acid well and is easy to prepare a highly uniform composition. 2-Imidazolidinone, N-ethyl-2-pyrrolidone and γ-butyrolactone are preferred, and N-methyl-2-pyrrolidone is more preferred.

  In addition, even if it is a solvent which does not dissolve polyamic acid alone, it can be used for the preparation of the composition as long as polyamic acid does not precipitate. In particular, ethyl cellosolve, butyl cellosolve, ethyl carbitol, butyl carbitol, ethyl carbitol acetate, ethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, 1-butoxy-2-propanol, 1-phenoxy -2-propanol, propylene glycol monoacetate, propylene glycol diacetate, propylene glycol-1-monomethyl ether-2-acetate, propylene glycol-1-monoethyl ether-2-acetate, dipropylene glycol, 2- (2-ethoxy Propoxy) A solvent having a low surface tension such as propanol, methyl lactate, ethyl lactate, n-propyl lactate, n-butyl lactate, isoamyl lactate and the like can be mixed appropriately. Thereby, it is known that the coating film uniformity is improved at the time of application to the substrate, and can be suitably used in the present invention.

  The method for preparing the composition for forming a release layer of the present invention is arbitrary. A preferable example of the preparation method includes a method of filtering the reaction solution containing the target polyamic acid obtained by the method described above. At this time, the filtrate may be diluted or concentrated if necessary for the purpose of adjusting the concentration. By adopting such a method, it is possible not only to reduce the contamination of impurities that can cause deterioration in the adhesion, peelability, etc. of the release layer produced from the resulting composition, but also to efficiently form a release layer forming composition. Can be obtained. The solvent used for dilution is not particularly limited, and specific examples thereof include those similar to the specific examples of the reaction solvent for the above reaction. The solvent used for dilution may be used singly or in combination of two or more.

  The concentration of the polyamic acid in the composition for forming a release layer of the present invention is appropriately set in consideration of the thickness of the release layer to be produced, the viscosity of the composition, etc., but is usually about 1 to 30% by mass, preferably It is about 1-20 mass%. By setting it as such a density | concentration, the peeling layer about 0.05-5 micrometers thick can be obtained with reproducibility. The concentration of the polyamic acid should be adjusted by adjusting the amount of diamine and tetracarboxylic dianhydride used as the raw material for the polyamic acid, adjusting the amount when the isolated polyamic acid is dissolved in the solvent, etc. Can do.

  The viscosity of the composition for forming a release layer of the present invention is appropriately set in consideration of the thickness of the release layer to be produced, etc., but in particular, a film having a thickness of about 0.05 to 5 μm can be obtained with good reproducibility. When intended, it is usually about 10 to 10,000 mPa · s at 25 ° C., preferably about 20 to 5,000 mPa · s.

  Here, the viscosity can be measured using a commercially available liquid viscosity measurement viscometer, for example, with reference to the procedure described in JIS K7117-2, at a temperature of the composition of 25 ° C. . Preferably, a conical plate type (cone plate type) rotational viscometer is used as the viscometer, and preferably the composition temperature is 25 ° C. using 1 ° 34 ′ × R24 as a standard cone rotor. It can be measured under the condition of ° C. An example of such a rotational viscometer is TVE-25L manufactured by Toki Sangyo Co., Ltd.

  In addition, the composition for peeling layer formation of this invention may contain the crosslinking agent etc. in order to improve film | membrane intensity | strength other than a polyamic acid and an organic solvent, for example.

  By applying the composition for forming a release layer of the present invention described above to a substrate, and heating the resulting coating to thermally imidize the polyamic acid, excellent adhesion to the substrate and appropriateness with the resin substrate It is possible to obtain a release layer made of a polyimide film having good adhesion and moderate peelability.

  When such a release layer of the present invention is formed on a substrate, the release layer may be formed on a partial surface of the substrate, or may be formed on the entire surface. As an aspect of forming a release layer on a part of the surface of the substrate, an embodiment in which the release layer is formed only within a predetermined range of the substrate surface, a release layer is formed in a pattern such as a dot pattern or a line and space pattern on the entire surface of the substrate. There are forms to be formed. In addition, in this invention, a base | substrate means what is used for manufacture of a flexible electronic device etc. by which the composition for peeling layer formation of this invention is applied to the surface.

  Examples of the substrate (substrate) include glass, plastic (polycarbonate, polymethacrylate, polystyrene, polyester, polyolefin, epoxy, melamine, triacetyl cellulose, ABS, AS, norbornene resin, etc.), metal (silicon wafer, etc.), Although wood, paper, slate, etc. are mentioned, since the peeling layer of this invention has sufficient adhesiveness with respect to it, glass is preferable. In addition, the base | substrate surface may be comprised with the single material and may be comprised with two or more materials. As an aspect 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 other surface is composed of other materials. A dot pattern is formed on the entire surface of the substrate. There is a mode in which a material in a pattern such as a line and space pattern is present in other materials.

  The method for applying the release layer-forming composition of the present invention to the substrate is not particularly limited, and examples thereof include cast coating, spin coating, blade coating, dip coating, roll coating, and bar coating. Method, die coating method, ink jet method, printing method (eg, relief printing, intaglio printing, planographic printing, screen printing, etc.).

  The heating temperature for imidization is usually appropriately determined within the range of 50 to 550 ° C, but is preferably more than 150 ° C to 510 ° C. By setting the heating temperature in this way, it is possible to sufficiently advance the imidization reaction while preventing the obtained film from being weakened. The heating time varies depending on the heating temperature and cannot be defined unconditionally, but is usually 5 minutes to 5 hours. Moreover, the imidation ratio should just be the range of 50 to 100%.

  As a preferable example of the heating mode in the present invention, after heating at 50 to 150 ° C. for 5 minutes to 2 hours, the heating temperature is gradually increased as it is, and finally from 150 ° C. to 510 ° C. for 30 minutes to 4 hours. The method of heating is mentioned. In particular, as a more preferable example of the heating mode, after heating at 50 to 100 ° C. for 5 minutes to 2 hours, more than 100 ° C. to 375 ° C. for 5 minutes to 2 hours, and finally more than 375 ° C. to 450 ° C. for 30 minutes to The method of heating for 4 hours is mentioned. Furthermore, as another more preferable example of the heating mode, after heating at 50 to 150 ° C. for 5 minutes to 2 hours, more than 150 ° C. to 350 ° C. for 5 minutes to 2 hours, then more than 350 ° C. to 450 ° C. for 30 minutes A method of heating at 450 ° C. to 510 ° C. for 30 minutes to 4 hours at the end of ˜4 hours is mentioned.

  Examples of the appliance used for heating include a hot plate and an oven. The heating atmosphere may be under air or under an inert gas, and may be under normal pressure or under reduced pressure.

  The thickness of the release layer is usually about 0.01 to 50 μm, and preferably about 0.05 to 20 μm from the viewpoint of productivity. In addition, desired thickness is implement | achieved by adjusting the thickness of the coating film before a heating.

  The release layer described above has excellent adhesion to a substrate, particularly a glass substrate, moderate adhesion to a resin substrate, and moderate release. Therefore, the release layer of the present invention peels the resin substrate from the substrate together with the circuit formed on the resin substrate without damaging the resin substrate of the device in the manufacturing process of the flexible electronic device. Therefore, it can be suitably used.

Hereinafter, an example of the manufacturing method of the flexible electronic device using the peeling layer of this invention is demonstrated.
Using the composition for forming a release layer of the present invention, a release layer is formed on a glass substrate by the method described above. A resin solution for forming a resin substrate is applied on the release layer, and this coating film is heated to form a resin substrate fixed to the glass substrate via the release layer of the present invention. At this time, the substrate is formed with a larger area than the area of the release layer so as to cover the entire release layer. Examples of the resin substrate include a resin substrate made of polyimide, which is a typical resin substrate for flexible electronic devices, and examples of the resin solution for forming the resin substrate include a polyimide solution and a polyamic acid solution. The method for forming the resin substrate may follow a conventional method.

  Next, a desired circuit is formed on the resin substrate fixed to the base via the release layer of the present invention, and then the resin substrate is cut along the release layer, for example. The resin substrate and the substrate are separated by peeling from the release layer. At this time, a part of the substrate may be cut together with the release layer.

  In JP 2013-147599 A, it is reported that the laser lift-off method (LLO method) that has been used in the manufacture of high-brightness LEDs, three-dimensional semiconductor packages and the like is applied to the manufacture of flexible displays. . The LLO method is characterized in that light having a specific wavelength, for example, light having a wavelength of 308 nm, is irradiated from the surface opposite to the surface on which a circuit or the like is formed from the glass substrate side. The irradiated light passes through the glass substrate, and only the polymer (polyimide) in the vicinity of the glass substrate absorbs this light and evaporates (sublimates). As a result, it is possible to selectively peel the resin substrate from the glass substrate without affecting the circuit or the like provided on the resin substrate, which determines the performance of the display.

  Since the composition for forming a release layer of the present invention has a feature of sufficiently absorbing light having a specific wavelength (for example, 308 nm) that enables application of the LLO method, it can be used as a sacrificial layer for the LLO method. Therefore, when a desired circuit is formed on a resin substrate fixed to a glass substrate through a release layer formed by using the composition according to the present invention, and then an LLO method is performed to irradiate a light beam of 308 nm. Only the release layer absorbs this light and evaporates (sublimates). Thereby, the release layer is sacrificed (acts as a sacrifice layer), and the resin substrate can be selectively peeled from the glass substrate.

EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated further in detail, this invention is not limited to these Examples.
[1] Abbreviations of compounds p-PDA: p-phenylenediamine DATP: 4,4 ″ -diamino-p-terphenyl TFMB: 2,2′-bis (trifluoromethyl) benzidine 6FAP: 2,2-bis ( 3-Amino-4-hydroxyphenyl) hexafluoropropane PMDA: pyromellitic dianhydride BPDA: 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride LS-3280: 4-aminophenoxydimethylvinylsilane LS -3150: 3-aminopropyltriethoxysilane TMA: trimellitic anhydride IHPA: isophthalaldehyde NMP: N-methyl-2-pyrrolidone

[2] Measurement of weight average molecular weight and molecular weight distribution The weight average molecular weight (hereinafter abbreviated as Mw) and molecular weight distribution of a polymer are measured by a GPC apparatus manufactured by JASCO Corporation (column: OHpak SB803-HQ manufactured by Shodex, and OHpak SB804-). HQ; eluent: dimethylformamide / LiBr.H ₂ O (29.6 mM) / H ₃ PO ₄ (29.6 mM) / THF (0.1 wt%); flow rate: 1.0 mL / min; column temperature: 40 ° C. Mw: standard polystyrene conversion value).

[3] Synthesis of Polymer <Synthesis Example F1 Synthesis of polyamic acid (F1)>
20.261 g (187 mmol) of p-PDA and 12.206 g (47 mmol) of DATP were dissolved in 617.4 g of NMP. The obtained solution was cooled to 15 ° C., 50.112 g (230 mmol) of PMDA was added thereto, and the temperature was raised to 50 ° C. in a nitrogen atmosphere and reacted for 48 hours. Mw of the obtained polymer was 82,100, and molecular weight distribution was 2.7.

<Synthesis Example F2 Synthesis of polyamic acid (F2)>
3.218 g (30 mmol) of p-PDA was dissolved in 88.2 g of NMP. To the obtained solution, 8.581 g (29 mmol) of BPDA was added and reacted at 23 ° C. for 24 hours under a nitrogen atmosphere. Mw of the obtained polymer was 107,300, and the molecular weight distribution was 4.6.

<Synthesis Example L1 Synthesis of polyamic acid (L1)>
2.66 g (24.6 mmol) of p-PDA and 0.18 g (0.6 mmol) of TFMB were dissolved in 90 g of NMP. PMDA 6.09 g (27.9 mmol) was added to the resulting solution and reacted at 23 ° C. for 24 hours under a nitrogen atmosphere, followed by addition of LS-3280 1.08 g (5.6 mmol) and further reaction for 24 hours. Thus, silyl groups were introduced at both ends of the polyamic acid. Mw of the obtained polymer was 62,700 and molecular weight distribution was 2.7.

<Synthesis Example L2 Synthesis of polyamic acid (L2)>
2.96 g (27.3 mmol) of p-PDA and 0.19 g (0.6 mmol) of TFMB were dissolved in 90 g of NMP. PMDA 6.34 g (29.1 mmol) was added to the resulting solution and reacted at 23 ° C. for 24 hours under a nitrogen atmosphere, and then LS-3150 0.52 g (2.3 mmol) was added and reacted for another 24 hours. Thus, silyl groups were introduced at both ends of the polyamic acid. Mw of the obtained polymer was 51,100 and molecular weight distribution was 2.8.

<Synthesis Example L3 Synthesis of polyamic acid (L3)>
p-PDA 3.06 (28.3 mmol) was dissolved in 90 g of NMP. PMDA 6.42g (29.4mmol) was added to the obtained solution and reacted at 23 ° C for 24 hours under a nitrogen atmosphere. Then, LS-3150 0.52g (2.4mmol) was added and reacted for another 24 hours. Thus, silyl groups were introduced at both ends of the polyamic acid. Mw of the obtained polymer was 47,800 and molecular weight distribution was 2.8.

<Synthesis Example L4 Synthesis of polyamic acid (L4)>
0.78 g (7.2 mmol) of p-PDA was dissolved in 17.6 g of NMP. To the obtained solution, 1.51 g (6.9 mmol) of PMDA was added and reacted at 23 ° C. for 24 hours under a nitrogen atmosphere, and then 0.11 g (0.3 mmol) of TMA was added and reacted for another 24 hours. Carboxylic acid groups were introduced at both ends of the polyamic acid. The obtained polymer had Mw of 48,000 and a molecular weight distribution of 3.1.

<Comparative Synthesis Example 1 Synthesis of Polybenzoxazole Precursor (B1)>
3.18 g (0.059 mol) of 6FAP was dissolved in 70 g of NMP. To the resulting solution, 7.92 g (0.060 mol) of IHPA was added and reacted at 23 ° C. for 24 hours under a nitrogen atmosphere. Mw of the obtained polymer was 107,300, and the molecular weight distribution was 4.6.

[4] Preparation of Resin Substrate Forming Composition The reaction solutions obtained in Synthesis Examples F1 and F2 were used as resin substrate forming compositions W and X, respectively.

[5] Preparation of release layer forming composition [Example 1-1]
6 g of NMP and 4 g of butyrocellosolve were added to 10 g of the reaction solution obtained in Synthesis Example L1, and the mixture was stirred at room temperature for 24 hours to obtain a release layer forming composition.

[Examples 1-2 to 1-3]
A composition for forming a release layer was obtained in the same manner as in Example 1-1, except that the reaction solutions obtained in Synthesis Examples L2 to L3 were used in place of the reaction solution obtained in Synthesis Example L1, respectively. It was.

[Example 1-4]
To 10 g of the reaction solution obtained in Synthesis Example L4, 9.4 g of NMP and 4.6 g of butyrocellosolve were added and stirred at room temperature for 24 hours to obtain a composition for forming a release layer.

[Comparative Example 1-1]
The reaction solution obtained in Comparative Synthesis Example 1 was diluted with NMP so that the polymer concentration was 5 wt% to obtain a composition.

[6] Formation of release layer and evaluation thereof [Example 2-1]
Using a spin coater (condition: about 3,000 rpm for about 30 seconds), the release layer forming composition obtained in Example 1-1 was placed on a 100 mm × 100 mm glass substrate (hereinafter the same) as a glass substrate. It was applied to.
The obtained coating film was heated at 80 ° C. for 10 minutes using a hot plate, and then heated at 300 ° C. for 30 minutes using an oven, and the heating temperature was raised to 400 ° C. (10 ° C./min. And then heated at 400 ° C. for 30 minutes to form a release layer having a thickness of about 0.1 μm on the glass substrate. During the temperature increase, the film-coated substrate was not removed from the oven but heated in the oven.

[Examples 2-2 to 2-4]
Example 2-1 except that the composition for forming a release layer obtained in Examples 1-2 to 1-4 was used in place of the composition for forming a release layer obtained in Example 1-1. A release layer was formed in the same manner as described above.

[Comparative Example 2-1]
A resin thin film was prepared in the same manner as in Example 2-1, except that the composition obtained in Comparative Example 1-1 was used instead of the release layer forming composition obtained in Example 1-1. Formed.

[7] Evaluation of peelability [Examples 3-1 to 3-4, Comparative example 3-1]
By the following method, the board | substrate was produced so that it might become a combination of the peeling layer shown in Table 1, and the resin substrate, and peelability was evaluated.
The peelability of the release layer and glass substrate obtained in Examples 2-1 to 2-4 and the peelability of the release layer (resin thin film) and the resin substrate were confirmed. As the resin substrate, a resin substrate made of polyimide was used.
First, cross-cutting of the release layer on the glass substrate with the release layer obtained in Examples 2-1 to 2-4 (1 mm in length and width, the same applies hereinafter), and the resin substrate on the resin substrate / glass substrate with the release layer -A 100 muscut was made by cross-cutting the release layer. That is, 100 crosses of 1 mm square were formed by this cross cut.
And the adhesive tape was stuck on this 100 muscat part, the tape was peeled off, and the degree of peeling was evaluated based on the following criteria (5B-0B, B, A, AA) (Examples 3-1 to 3- 4). Moreover, according to the said method, the same test was done using the glass substrate with a resin thin film obtained by Comparative Example 2-1 (Comparative Example 3-1). The results are shown in Table 1.

5B: 0% peeling (no peeling)
4B: Less than 5% peeling 3B: Less than 5-15% peeling 2B: 15-35% peeling 1B: 35-65% peeling 0B: 65% -80% peeling B: 80% -95 % Peeling A: 95% to less than 100% peeling AA: 100% peeling (all peeling)

In addition, the resin substrate of Examples 3-1 to 3-4 and Comparative Example 3-1 was formed by the following method.
Using a bar coater (gap: 250 μm), either the resin substrate forming composition W or X was applied on the release layer (resin thin film) on the glass substrate. The obtained coating film was heated at 80 ° C. for 10 minutes using a hot plate, and then heated at 140 ° C. for 30 minutes using an oven, and the heating temperature was raised to 210 ° C. (10 ° C./min. The same applies to the following, and the heating temperature was raised to 210 ° C. for 30 minutes, the heating temperature was raised to 300 ° C., the heating temperature was raised to 300 ° C. for 30 minutes, the heating temperature was raised to 400 ° C., and the heating temperature was raised to 400 ° C. for 60 minutes. A polyimide substrate having a thickness of about 20 μm was formed. During the temperature increase, the film-coated substrate was not removed from the oven but heated in the oven.

  As Table 1 shows, it turns out that the peeling layer of an Example is excellent in adhesiveness with a glass substrate, and excellent in peelability with a resin substrate. On the other hand, the resin thin film of the comparative example was found to adhere to the resin layer and not peel at all when the adhesion between the glass substrate and the release layer was low or the adhesion was high.

Claims (8)

  A composition for forming a release layer comprising a polyamic acid obtained by introducing an anchor group into either one or both of the polymer chain ends and an organic solvent.   The composition for forming a release layer according to claim 1, wherein the anchor group is a silyl group or a carboxylic acid group.   The polyamic acid is a polyamic acid obtained by reacting a diamine component containing an aromatic diamine and an acid dianhydride component containing an aromatic tetracarboxylic dianhydride. The composition for peeling layer formation of description.   The composition for forming a release layer according to claim 3, wherein the aromatic diamine is an aromatic diamine containing 1 to 5 benzene nuclei.   The release layer forming composition according to claim 3 or 4, wherein the aromatic tetracarboxylic dianhydride is an aromatic tetracarboxylic dianhydride containing 1 to 5 benzene nuclei.   The peeling layer formed using the composition for peeling layer formation of any one of Claims 1-5.   A method for producing a flexible electronic device comprising a resin substrate, wherein the release layer according to claim 6 is used.   The manufacturing method according to claim 7, wherein the resin substrate is a substrate made of polyimide.