Classifications

• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
  • C09J175/02—Polyureas
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/40—Layered products comprising a layer of synthetic resin comprising polyurethanes
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
  • B32B7/04—Interconnection of layers
  • B32B7/06—Interconnection of layers permitting easy separation
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
  • C08K5/0025—Crosslinking or vulcanising agents; including accelerators
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/04—Oxygen-containing compounds
  • C08K5/13—Phenols; Phenolates
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/16—Nitrogen-containing compounds
  • C08K5/34—Heterocyclic compounds having nitrogen in the ring
  • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
  • C08K5/3472—Five-membered rings
  • C08K5/3475—Five-membered rings condensed with carbocyclic rings
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/16—Nitrogen-containing compounds
  • C08K5/34—Heterocyclic compounds having nitrogen in the ring
  • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
  • C08K5/3477—Six-membered rings
  • C08K5/3492—Triazines
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
  • C08K5/41—Compounds containing sulfur bound to oxygen
  • C08K5/42—Sulfonic acids; Derivatives thereof
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
  • C08L33/04—Homopolymers or copolymers of esters
  • C08L33/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
  • C08L75/02—Polyureas
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
  • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
  • C09J11/02—Non-macromolecular additives
  • C09J11/06—Non-macromolecular additives organic
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
  • C09J11/08—Macromolecular additives
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K3/00—Materials not provided for elsewhere

Definitions

• the present invention relates to a composition for forming a release layer and a release layer.
• the metal nanowire dispersion liquid has a low viscosity, it is difficult to apply it by ordinary screen printing or letterpress printing.
• a thickener or the like is added to the metal nanowire dispersion liquid in order to increase the viscosity, it is possible to apply by printing, but the non-conductor thickener remains in the coating film after drying. , There was a problem of hindering conductivity. Since the genus nanowire dispersion has a low viscosity, it is difficult to apply it by ordinary screen printing or letterpress printing.
• the base material of the touch panel film is also changed from glass to a sheet made of plastic such as polyethylene terephthalate (PET), polyimide, cycloolefin, and acrylic, and a transparent flexible touch screen panel having flexibility has been developed.
• PET polyethylene terephthalate
• acrylic polyimide
• cycloolefin cycloolefin
• acrylic acrylic
• a transparent flexible touch screen panel having flexibility has been developed.
• a base material capable of withstanding a high temperature process is required (Patent Documents 6 to 8).
• a peel (adhesive) layer is formed on a support substrate such as a glass substrate, and a device is formed on the peeling (adhesive) layer and then peeled.
• This peeling layer must not be peeled from the support substrate during the process, but a low peeling force is required when peeling.
• the present invention has been made in view of the above circumstances, and is a release layer having high heat resistance and appropriate peelability, having constant peelability even through a high temperature process, and excellent stability after film formation. It is an object of the present invention to provide a composition for forming a release layer.
• the present inventors have (A) polyurea containing a predetermined repeating unit, (B) an acid compound or a salt thereof, (C) a hydroxyalkyl group and / or an alkoxy.
• a cross-linking agent selected from a compound having a nitrogen atom substituted with a methyl group, (D) a polymer additive containing a predetermined repeating unit, and (E) a composition for forming a release layer containing a solvent have high heat resistance.
• the present invention has been completed by finding that a release layer having excellent adhesion to a substrate, appropriate adhesion to a resin substrate, and appropriate peelability can be provided with good reproducibility.
• the present invention provides the following composition for forming a release layer and a release layer.
• 1. Polyurea containing a repeating unit represented by the following formula (1), (B) Acid compound or salt thereof, (C) A cross-linking agent selected from compounds having a nitrogen atom substituted with a hydroxyalkyl group and / or an alkoxymethyl group.
• D A polymer additive containing a repeating unit represented by the following formula (a), a repeating unit represented by the following formula (b) and a repeating unit represented by the following formula (c), and a solvent (E).
• a 1 , A 2 , A 3 , A 4 , A 5 and A 6 are independently hydrogen atoms, methyl groups or ethyl groups, respectively.
• X 1 is a group represented by the following formulas (1-1), (1-2), (1-3) or (1-4).
• R 1 and R 2 are independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 3 to 6 carbon atoms, a benzyl group or a phenyl group, and the phenyl group is carbon.
• R 1 and R 2 may be bonded to each other to form a ring having 3 to 6 carbon atoms together with the carbon atom to which they are bonded, and R 3 has 1 to 6 carbon atoms.
• Q 1 is a group represented by the following formula (1-5) or (1-6).
• X 2 is a group represented by the formula (1-1), the formula (1-2) or the formula (1-4), and Q 2 is an alkylene group having 1 to 10 carbon atoms, phenylene.
• the phenylene group, naphthylene group and anthrylene group are a group, a naphthylene group or an anthrylene group, and the phenylene group, the naphthylene group and the anthrylene group are an alkyl group having 1 to 6 carbon atoms, a halogen atom, an alkoxy group having 1 to 6 carbon atoms, a nitro group, a cyano group and a hydroxy group.
• R A is independently, a hydrogen atom or a methyl group
• R B is at least one branched alkyl group of which a hydrogen atom is 3 or 4 carbon atoms are substituted with fluorine atoms
• RC is a polycyclic alkyl group having 1 to 4 hydroxy groups and having 6 to 20 carbon atoms
• RD is a polycyclic alkyl group having 6 to 20 carbon atoms or 6 to 12 carbon atoms. It is an aryl group of.
• R 11 to R 34 are independently hydrogen atoms or alkyl groups having 1 to 6 carbon atoms, but alkyl groups having 1 to 6 carbon atoms are preferable.
• R 35 is a hydrogen atom or methyl group.
• 7. The resin composition for forming a release layer according to any one of 1 to 6, wherein the content of the (C) cross-linking agent is 5 to 50 parts by mass with respect to 100 parts by mass of (A) polyurea.
• RC is a resin composition for forming a release layer according to any one of 1 to 7, which has an adamantane structure.
• a method for producing a resin substrate which comprises a step and a step of peeling the resin substrate with a peeling force of 0.25 N / 25 mm or less.
• the composition for forming a release layer of the present invention By using the composition for forming a release layer of the present invention, it is possible to obtain a release layer having high heat resistance, excellent adhesion to a substrate, appropriate adhesion to a resin substrate, and appropriate peelability with good reproducibility. it can. Further, in the manufacturing process of a flexible electronic device, it is possible to separate the resin substrate from the substrate together with the circuit, etc. without damaging the resin substrate formed on the substrate, the circuit provided on the resin substrate, or the like. It will be possible. Therefore, the composition for forming a release layer of the present invention can contribute to speeding up the manufacturing process of a flexible electronic device including a resin substrate and improving the yield thereof.
• composition for forming a release layer of the present invention comprises (A) a polyurea containing a predetermined repeating unit, (B) an acid compound or a salt thereof, and (C) a nitrogen atom substituted with a hydroxyalkyl group and / or an alkoxymethyl group. It contains a cross-linking agent selected from the compounds having the compound, (D) a polymer additive containing a predetermined repeating unit, and (E) a solvent.
• the polyurea of the component (A) contains a repeating unit represented by the following formula (1).
• a 1 , A 2 , A 3 , A 4 , A 5 and A 6 are each independently a hydrogen atom, a methyl group or an ethyl group, but from the viewpoint of peelability and productivity, It is preferable that A 1 to A 6 are all hydrogen atoms.
• X 1 is a group represented by the following formulas (1-1), (1-2), (1-3) or (1-4).
• R 1 and R 2 are independently hydrogen atoms, alkyl groups having 1 to 6 carbon atoms, alkoxy groups having 3 to 6 carbon atoms, benzyl groups or phenyls, respectively.
• the phenyl group is a group consisting of an alkyl group having 1 to 6 carbon atoms, a halogen atom, an alkoxy group having 1 to 6 carbon atoms, a nitro group, a cyano group, a hydroxy group and an alkylthio group having 1 to 6 carbon atoms. It may be substituted with at least one group selected from, and R 1 and R 2 may be bonded to each other to form a ring having 3 to 6 carbon atoms together with the carbon atom to which they are bonded.
• R 3 is an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 3 to 6 carbon atoms, a benzyl group or a phenyl group, and the phenyl group is an alkyl group having 1 to 6 carbon atoms. It may be substituted with at least one group selected from the group consisting of a group, a halogen atom, an alkoxy group having 1 to 6 carbon atoms, a nitro group, a cyano group, a hydroxy group and an alkylthio group having 1 to 6 carbon atoms.
• Q 1 is a group represented by the following formula (1-5) or (1-6).
• X 2 is a group represented by formula (1-1), formula (1-2) or formula (1-4).
• formula (1-5 for example, when X 2 is a group represented by formula (1-2), its structure is formula (1-5-1). (In the formula, R 1 and R 2 are the same as above.)
• Q 2 is an alkylene group having 1 to 10 carbon atoms, a phenylene group, a naphthylene group or an anthrylene group.
• the phenylene group, naphthylene group and anthrylene group are an alkyl group having 1 to 6 carbon atoms, a halogen atom, an alkoxy group having 1 to 6 carbon atoms, a nitro group, a cyano group, a hydroxy group and an alkylthio group having 1 to 6 carbon atoms. It may be substituted with at least one group selected from the group consisting of.
• the position of their bond is not particularly limited. That is, for example, when the phenylene group is bonded at the 1-position and the 2-position, when it is bonded at the 1-position and the 3-position, or when it is bonded at the 1-position and the 4-position, the naphthalene group is 1 When bonded at the 2-position, bonded at the 1-position and 4-position, bonded at the 1-position and 5-position, or bonded at the 2-position and 3-position, the anthrylene group is bonded. It may be bonded at the 1st position and the 2nd position, bonded at the 1st position and the 4th position, or bonded at the 9th position and the 10th position, but any of them may be used.
• the alkyl group having 1 to 6 carbon atoms may be linear, branched or cyclic, and examples thereof include a methyl group, an ethyl group, an isopropyl group, an n-butyl group and a cyclohexyl group.
• the alkenyl group having 3 to 6 carbon atoms may be linear, branched or cyclic, and examples thereof include a 2-propenyl group and a 3-butenyl group.
• the alkoxy group having 1 to 6 carbon atoms may be linear, branched or cyclic, and examples thereof include a methoxy group, an ethoxy group, an isopropoxy group, an n-pentyloxy group and a cyclohexyloxy group. ..
• the alkylthio group having 1 to 6 carbon atoms may be linear, branched or cyclic, and examples thereof include a methylthio group, an ethylthio group, an isopropylthio group, an n-pentylthio group and a cyclohexylthio group.
• halogen atom examples include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
• ring having 3 to 6 carbon atoms formed by combining R 1 and R 2 include a cyclobutane ring, a cyclopentane ring, and a cyclohexane ring.
• the alkylene group having 1 to 10 carbon atoms may be linear, branched or cyclic, and may be, for example, a methylene group, an ethylene group, a propylene group, a pentamethylene group, a cyclohexylene group, a 2-methylpropylene group or the like. Can be mentioned.
• Q 1 preferably contains a cyclic structure from the viewpoint of heat resistance of the polyurea component (A). That is, Q 1 is a group represented by the formula (1-5) or a group represented by the formula (1-6), and Q 2 is a cyclic alkylene group, a phenylene group, a naphthylene group or an anthrylene group. It is preferable, and it is more preferable that it is a group represented by the formula (1-5).
• the polyurea of the component (A) can be synthesized with reference to, for example, International Publication No. 2005/098542.
• the weight average molecular weight (Mw) of (A) polyurea is preferably 1,000 to 200,000, more preferably 3,000 to 100,000, even more preferably 4,000 to 30,000, and 5,000 to 5,000. 20,000 is even more preferred.
• the dispersity (Mw / Mn) is preferably 1.3 to 4.0, more preferably 1.4 to 2.5.
• Mn is a number average molecular weight, and Mw and Mn are polystyrene-equivalent measured values by gel permeation chromatography (GPC).
• the composition for forming a release layer of the present invention contains an acid compound or a salt thereof as the component (B).
• the acid compound include p-toluenesulfonic acid, trifluoromethanesulfonic acid, pyridinium-p-toluenesulfonate, salicylic acid, camphorsulfonic acid, sulfosalicylic acid, 4-chlorobenzenesulfonic acid, 4-hydroxybenzenesulfonic acid, and benzenedisulfonic acid.
• Examples thereof include sulfonic acid compounds such as 1-naphthalene sulfonic acid and pyridinium-1-naphthalene sulfonic acid, and carboxylic acid compounds such as salicylic acid, sulfosalicylic acid, citric acid, benzoic acid and hydroxybenzoic acid.
• Examples of the salt of the acid compound include pyridinium salt, isopropanolamine salt, N-methylmorpholin salt and the like of the acid, and specific examples thereof include pyridinium p-toluenesulfonate, pyridinium 1-naphthalenesulfonate and isopropanol. Amine p-toluene sulfonate, N-methylmorpholine p-toluene sulfonate and the like can be mentioned.
• the content of the component (B) is preferably 0.01 to 15 parts by mass, more preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the polyurea of the component (A).
• the acid compound (B) or a salt thereof may be used alone or in combination of two or more.
• the composition for forming a release layer of the present invention contains a cross-linking agent as the component (C).
• the cross-linking agent is selected from compounds having a nitrogen atom substituted with a hydroxyalkyl group and / or an alkoxymethyl group.
• cross-linking agent a compound represented by any of the following formulas (C-1) to (C-7) is preferable.
• R 11 to R 34 are independently hydrogen atoms or alkyl groups having 1 to 6 carbon atoms, but alkyl groups having 1 to 6 carbon atoms are preferable.
• R 35 is a hydrogen atom or a methyl group.
• cross-linking agent hexamethylol melamine, tetramethylol benzoguanamine, 1,3,4,6-tetramethylol glycol uryl, hexamethoxymethylmelamine, tetramethoxymethylbenzoguanamine, 1,3,4,6-tetrakis
• nitrogen-containing compounds such as methoxymethyl) glycol uryl, 1,3,4,6-tetrakis (butoxymethyl) glycol uryl, and 1,3,4,6-tetrakis (hydroxymethyl) glycol uryl.
• methoxymethyl type melamine compounds manufactured by Ornex (trade names: Cymel (registered trademark) 300, Cymel 301, Cymel 303, Cymel 350), butoxymethyl type melamine compounds (trade names: Mycoat (registered trademark) 506, Mycoat 508).
• Glycoluryl compound (trade name: Cymel 1170, POWDERLINK 1174), methylated urea resin (trade name: UFR65), butylated urea resin (trade name: UFR300, U-VAN10S60, U-VAN10R, U-VAN11HV), DIC Co., Ltd.
• nitrogen-containing compounds such as urea / formaldehyde-based resins (trade names: Beccamin (registered trademark) J-300S, Beccamin P-955, Beccamin N).
• cross-linking agent 3,3'-5,5'-tetrakis (methoxymethyl)-[1,1'-biphenyl] -4,4'-diol, 5,5'-(1-methylethylidene) bis.
• aromatic ring compounds such as [2-hydroxy-1,3-benzenedimethanol].
• a hydroxymethyl group or an alkoxymethyl group such as N-hydroxymethyl (meth) acrylamide, N-methoxymethyl (meth) acrylamide, N-ethoxymethyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide and the like.
• Polymers made using (meth) acrylamide compounds substituted with are available. Such polymers include, for example, poly (N-butoxymethyl (meth) acrylamide), N-butoxymethyl (meth) acrylamide and styrene copolymers, N-hydroxymethyl (meth) acrylamide and methyl (meth).
• the cross-linking agent is hexamethoxymethylmelamine, tetramethoxymethylbenzoguanamine, 1,3,4,6-tetrakis (methoxymethyl) glycoluryl (POWDERLINK 1174), 1,3,4,6-tetrakis (butoxymethyl).
• Glycoluryl, 1,3,4,6-tetrakis (hydroxymethyl) glycoluryl can be mentioned.
• cross-linking agents can cause a cross-linking reaction by self-condensation.
• a cross-linking reaction can occur with the hydroxy group in the polyurea of the component (A). Then, by such a cross-linking reaction, the formed release layer becomes strong and becomes a release layer having low solubility in an organic solvent.
• the content of the component (C) is preferably 5 to 100 parts by mass, more preferably 10 to 50 parts by mass, based on 100 parts by mass of the polyurea of the component (A).
• the content of the component (C) is within the above range, a composition having high heat resistance and appropriate peelability and capable of providing a peeling layer having excellent stability after film formation can be obtained.
• the cross-linking agent may be used alone or in combination of two or more.
• composition for forming a release layer of the present invention has a repeating unit represented by the following formula (a), a repeating unit represented by the following formula (b), and a repeating unit represented by the following formula (c) as a component (D).
• a a repeating unit represented by the following formula (a)
• b a repeating unit represented by the following formula (b)
• c a repeating unit represented by the following formula (c) as a component (D).
• RA is independently a hydrogen atom or a methyl group.
• R B is at least one branched alkyl group of which a hydrogen atom is 3 or 4 carbon atoms are substituted with fluorine atoms.
• RC is a polycyclic alkyl group having 1 to 4 hydroxy groups and 6 to 20 carbon atoms.
• RD is a polycyclic alkyl group having 6 to 20 carbon atoms or an aryl group having 6 to 12 carbon atoms.
• Examples of the branched alkyl group having 3 or 4 carbon atoms include an isopropyl group, an isobutyl group, a sec-butyl group and a tert-butyl group.
• the R B are preferred in which at least one hydrogen atom of these branched alkyl group have been substituted with fluorine atoms, specific examples include 1,1,1-trifluoro-isopropyl group, 1,1,1, Examples thereof include 3,3,3-hexafluoroisopropyl group and nonafluorotert-butyl group.
• Examples of the polycyclic alkyl group having 6 to 20 carbon atoms include a 1-adamantyl group, a 2-adamantyl group, an isobornyl group, a norbornyl group and the like.
• Examples of the polycyclic alkyl group having 1 to 4 hydroxy groups and 6 to 20 carbon atoms include a group in which these groups are substituted with a hydroxy group.
• Examples of the aryl group having 6 to 12 carbon atoms include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 1-biphenylyl group, a 2-biphenylyl group and the like.
• Examples of the repeating unit represented by the formula (a) include, but are not limited to, those represented by the following formulas (a-1) to (a-3).
• RA is the same as described above.
• Examples of the repeating unit represented by the formula (b) include, but are not limited to, those represented by the following formulas (b-1) to (b-27).
• RA is the same as described above.
• Examples of the repeating unit represented by the formula (c) include, but are not limited to, those represented by the following formulas (c-1) to (c-13).
• RA is the same as described above.
• the content of the repeating unit represented by the formula (a) is preferably 15 to 60 mol%, more preferably 20 to 55 mol%, of all the repeating units.
• the content of the repeating unit represented by the formula (b) is preferably 8 to 38 mol%, more preferably 10 to 38 mol%, of all the repeating units.
• the content of the repeating unit represented by the formula (c) is preferably 2 to 77 mol%, more preferably 5 to 67 mol%, of all the repeating units.
• the Mw of the polymer additive (D) is preferably 2,000 to 20,000, more preferably 2,500 to 15,000.
• the Mw / Mn thereof is preferably 1.0 to 2.5, more preferably 1.0 to 2.3.
• the content of the polymer additive of the component (D) is 3 to 100 parts by mass, preferably 3 to 80 parts by mass, and more preferably 3 to 50 parts by mass with respect to 100 parts by mass of the polyurea of the component (A). Is. If the content of the polymer additive is less than 3 parts by mass, the peeling force may increase, and if it exceeds 100 parts by mass, it may repel during film formation.
• the polymer additive may be used alone or in combination of two or more.
• the composition for forming a release layer of the present invention contains a solvent as the component (E).
• a solvent a glycol ether solvent having 3 to 20 carbon atoms, an ester solvent having 3 to 20 carbon atoms, a ketone solvent having 3 to 20 carbon atoms, or a cyclic compound solvent having 3 to 20 carbon atoms is preferable.
• glycol ether-based solvent examples include propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, ethylene glycol monomethyl ether, and ethylene glycol dimethyl ether.
• Ethylene glycol diethyl ether ethylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether (Digglyme), diethylene glycol diethyl ether, diethylene glycol monohexyl ether, diethylene glycol butyl methyl ether, triethylene glycol monomethyl ether, triethylene glycol Didimethyl ether, diethylene glycol monobutyl ether, diethylene glycol ethyl methyl ether, diethylene glycol isopropyl methyl ether, diethylene glycol dibutyl ether, dimethoxytetraethylene glycol, dipropylene glycol methyl ether, dipropylene glycol dimethyl ether, dipropylene glycol monomethyl ether, diethylene glycol monoethyl ether ace Examples thereof include tart, methoxymethylbutanol, tripropylene glycol dimethyl ether, and triethylene glycol but
• ester solvent examples include ethyl acetate, butyl acetate, methoxybutyl acetate, amyl acetate, isopropyl acetate, methyl lactate, ethyl lactate (EL), butyl lactate, methyl 2-hydroxyisobutyrate, ethyl 2-hydroxyisobutyrate, 3 -Ethyl ethoxypropionate and the like can be mentioned.
• ketone solvent examples include methyl ethyl ketone, methyl propyl ketone, methyl isobutyl ketone, diisobutyl ketone, diacetone alcohol, cyclohexanone, cyclopentanone, benzophenone and the like.
• Examples of the cyclic compound solvent include tetrahydrofuran, 1,4-dioxane, 1,3-dioxolane, 2-pyrrolidone, N-methylpyrrolidone, N-ethylpyrrolidone, 1,3-dimethyl-2-imidazolidinone, and ⁇ -butyrolactone. And so on.
• the content of the solvent (E) is preferably such that the solid content concentration in the composition for forming a release layer of the present invention is 0.1 to 40% by mass, more preferably 0.5 to 20% by mass. It is preferable, and an amount of 0.5 to 10% by mass is even more preferable.
• the solid content is a general term for all the components of the composition for forming a release layer other than the solvent.
• the solvent (E) may be used alone or in combination of two or more.
• the composition for forming a release layer of the present invention may contain a surfactant, if necessary.
• a surfactant By adding a surfactant, the applicability of the release layer forming composition to the substrate can be improved.
• known surfactants such as nonionic surfactants, fluorine-based surfactants, and silicone-based surfactants can be used.
• nonionic surfactant examples include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, and polyoxyethylene oleyl ether; polyoxyethylene octyl.
• Polyoxyethylene alkylaryl ethers such as phenyl ethers and polyoxyethylene nonylphenyl ethers; polyoxyethylene / polyoxypropylene block copolymers; sorbitan monolaurates, sorbitan monopalmitates, sorbitan monostearates, sorbitan monooleates, Solbitan fatty acid esters such as sorbitan trioleate and sorbitan tristearate; polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, polyoxyethylene sorbitan. Examples thereof include polyoxyethylene sorbitan fatty acid esters such as tristearate.
• fluorine-based surfactants examples include Ftop (registered trademark) EF301, EF303, EF352 (manufactured by Mitsubishi Materials Electronics Chemical Co., Ltd.), Megafuck (registered trademark) F171, F173, F251, F411, F444, and F477.
• silicone-based surfactant examples include organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.).
• composition for forming a release layer contains a surfactant
• the content thereof is preferably 0.0001 to 5 parts by mass, more preferably 0.001 to 3 parts by mass with respect to 100 parts by mass of (A) polyurea. ..
• the surfactant may be used alone or in combination of two or more.
• composition for forming a release layer The method for preparing the composition for forming a release layer of the present invention is not particularly limited.
• a preparation method for example, the component (B), the component (C), the component (D), the component (E) and the like are mixed in a solution of the component (A) dissolved in a solvent at a predetermined ratio to obtain a uniform solution. And a method of further adding and mixing other additives as needed at an appropriate stage of the above-mentioned preparation method.
• a solution of a specific copolymer (polymer) obtained by a polymerization reaction in a solvent can be used as it is.
• the component (B), the component (C), the component (D), the component (E) and the like are added to the solution of the component (A) in the same manner as described above to obtain a uniform solution.
• an additional solvent may be added for the purpose of adjusting the concentration.
• the solvent used in the process of producing the component (A) and the solvent used for adjusting the concentration of the composition for forming the release layer may be the same or different.
• the prepared solution of the release layer forming composition is used after being filtered using a filter or the like having a pore size of about 0.2 ⁇ m.
• the viscosity of the release layer forming composition 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 0.01 to 5 ⁇ m can be obtained with good reproducibility. Usually, it is about 0.5 to 5,000 mPa ⁇ s, preferably about 1 to 2,000 mPa ⁇ s at 25 ° C.
• the viscosity can be measured using a commercially available viscometer for measuring the viscosity of a liquid, for example, with reference to the procedure described in JIS K7117-2, under the condition that the temperature of the composition is 25 ° C. ..
• a conical plate type (cone plate type) rotational viscometer is used as the viscometer, and 1 ° 34'x R24 is preferably used as the standard cone rotor with the same type viscometer, and the temperature of the composition is 25. It can be measured under the condition of ° C.
• Examples of such a rotational viscometer include TVE-25L manufactured by Toki Sangyo Co., Ltd.
• the heating time cannot be unconditionally specified because it depends on the heating temperature, but it is usually 1 minute to 5 hours.
• the firing temperature may include a step of firing at a temperature lower than that as long as the maximum temperature is within the above range.
• the heating mode in the present invention there is a mode in which heating is performed at 50 to 150 ° C. for 1 minute to 1 hour, and then the heating temperature is raised as it is to heat at 180 to 280 ° C. for 5 minutes to 4 hours.
• the heating mode there is an aspect of heating at 50 to 150 ° C. for 1 minute to 1 hour and heating at 200 to 280 ° C. for 5 minutes to 2 hours.
• the release layer of the present invention When the release layer of the present invention is formed on the substrate, the release layer may be formed on a part surface of the substrate or may be formed on the entire surface. Examples of forming the release layer on a part of the surface of the substrate include forming the release layer only in a predetermined range on the surface of the substrate, and forming the release layer in a pattern such as a dot pattern or a line-and-space pattern on the entire surface of the substrate. There are modes of formation and the like.
• the substrate means a substrate on which the composition for forming a release layer of the present invention is coated, which is used for manufacturing a flexible electronic device or the like.
• the substrate examples include glass, metal (silicon wafer, etc.), slate, and the like.
• the release layer obtained from the composition for forming a release layer of the present invention has sufficient adhesion to the substrate. Glass is preferable because it has.
• the surface of the substrate may be made of a single material or may be made of two or more materials. A mode in which the surface of the substrate is composed of two or more materials is a mode in which a certain range of the surface of the substrate is composed of a certain material and the remaining surface is composed of other materials, a dot pattern on the entire surface of the substrate. , Line-and-space pattern, and other patterns in which the material is present in other materials.
• the coating method is not particularly limited, but for example, a cast coating method, a spin coating method, a blade coating method, a dip coating method, a roll coating method, a bar coating method, a die coating method, an inkjet method, and a printing method (letter plate, intaglio plate, planographic plate). , Screen printing, etc.).
• appliances used for heating include hot plates, ovens, and the like.
• the heating atmosphere may be under air or an inert gas, and may be under normal pressure or reduced pressure.
• the thickness of the release layer is usually about 0.01 to 50 ⁇ m, preferably about 0.01 to 20 ⁇ m, more preferably about 0.01 to 5 ⁇ m from the viewpoint of productivity, and the thickness of the coating film before heating. To achieve the desired thickness.
• the release layer of the present invention has excellent adhesion to a substrate, particularly a glass substrate, as well as appropriate adhesion to a resin substrate and appropriate peelability. Therefore, the release layer of the present invention detaches the resin substrate from the substrate together with the circuit and the like formed on the resin substrate without damaging the resin substrate of the device in the manufacturing process of the flexible electronic device. It can be preferably used to make it.
• the release layer forming composition of the present invention is used to form a release layer on the glass substrate by the above-mentioned method.
• the resin substrate forming solution for forming a resin substrate on the release layer and firing the obtained coating film the resin fixed to the glass substrate via the release layer of the present invention. Form a substrate.
• the firing temperature of the coating film is appropriately set according to the type of resin and the like, but in the present invention, the maximum temperature at the time of firing is preferably 180 to 280 ° C, preferably 190 to 270 ° C. It is more preferable to set the temperature at 200 to 250 ° C.
• the maximum temperature at the time of firing during the production of the resin substrate within this range, the adhesion between the release layer as the base and the substrate, and the appropriate adhesion and peelability between the release layer and the resin substrate are further improved. be able to. In this case as well, as long as the maximum temperature is within the above range, the step of firing at a temperature lower than that may be included.
• the resin substrate covers the entire release layer, and the resin substrate is formed in an area larger than the area of the release layer.
• the resin substrate include a resin substrate made of an acrylic polymer and a resin substrate made of a cycloolefin polymer.
• the method for forming the resin substrate may be a conventional method.
• the resin substrate preferably has a light transmittance of 80% or more at a wavelength of 400 nm.
• a desired circuit is formed on the resin substrate fixed to the substrate via the release layer of the present invention, if necessary, and then, for example, the resin substrate is cut along the release layer, and this circuit is formed.
• the resin substrate is peeled from the release layer to separate the resin substrate and the substrate.
• a part of the substrate may be cut together with the release layer.
• the resin substrate can be peeled from the release layer with a release force of 0.25 N / 25 mm or less, more preferably 0.15 N / 25 mm or less, still more preferably 0.1 N / 25 mm or less. it can.
• PGME Propylene Glycol Monomethyl Ether
• PGMEA Propylene Glycol Monomethyl Ether Acetate
• PL-LI 1,3,4,6-tetrax (methoxyethyl) glycoluryl (manufactured by Ornex, trade name: POWDERLINK 1174)
• PPTS P-toluenesulfonate pyridinium
• HPMA 2-hydroxypropyl methacrylate
• HEMA 2-hydroxyethyl methacrylate
• ADMA 2-adamantyl methacrylate
• CHMI cyclohexyl maleimide
• HFiPMA 1,1,1,3,3,3 methacrylic acid -HexafluoroisopropylPFHMA: 2- (perfluorohexyl) ethyl methacrylate
• KBM-503 3-methacryloxypropyltriethoxysilane
• HADM 3-hydroxy-1-adamantyl DHADM: 3,5-di
• the weight average molecular weight (Mw) of the polymer was measured by a GPC apparatus manufactured by Shimadzu Corporation (column: Shodex® KF803L and KF804L (manufactured by Showa Denko KK); eluent: tetrahydrofuran; flow rate: 1. It was carried out using 0.0 mL / min; column temperature: 40 ° C.; Mw: standard polystyrene conversion value).
• composition F1 for forming a resin substrate In an eggplant flask containing 100 g of carbon tetrachloride, 10 g of Zeonoa (registered trademark) 1020R (cycloolefin polymer manufactured by Nippon Zeon Corporation) and Epolide (registered trademark) GT401 3 g (manufactured by Daicel Corporation) was added. This solution was stirred and dissolved in a nitrogen atmosphere for 24 hours to prepare a resin substrate forming composition F1.
• Zeonoa registered trademark
• Epolide registered trademark
• Zeonoa registered trademark
• 1060R cycloolefin polymer manufactured by Nippon Zeon Corporation
• composition for forming a release layer [Example 1-1] Preparation of composition 1 for forming a release layer PL-LI 0.06 g, PPTS 0.01 g, and acrylic were added to 1 g of the reaction solution obtained in Synthesis Example 1. 0.08 g of a polymer (S1) solution and PGMEA were added and diluted with PGMEA so that the solid content concentration was 5% by mass and the PGMEA concentration was 30% by mass to prepare a release layer forming composition 1.
• Example 1-2 Preparation of composition 2 for forming a peeling layer Peeling is performed in the same manner as in Example 1-1 except that an acrylic polymer (S2) solution is used instead of the acrylic polymer (S1) solution.
• S2 acrylic polymer
• S1 acrylic polymer
• Example 1-3 Preparation of composition 3 for forming a release layer Peeling is performed in the same manner as in Example 1-1 except that an acrylic polymer (S3) solution is used instead of the acrylic polymer (S1) solution.
• S3 solution is used instead of the acrylic polymer (S1) solution.
• S1 solution was prepared.
• composition 4 for forming a release layer Peeling is performed in the same manner as in Example 1-1 except that an acrylic polymer (S4) solution is used instead of the acrylic polymer (S1) solution.
• S4 solution is used instead of the acrylic polymer (S1) solution.
• S1 solution is used instead of the acrylic polymer (S1) solution.
• the layer-forming composition 4 was prepared.
• composition 5 for forming a release layer PL-LI 0.04 g, PPTS 0.01 g, acrylic polymer (S5) solution 0.05 g, and PGMEA were added to 1 g of the reaction solution obtained in Synthesis Example 1.
• composition 7 for forming a release layer PGMEA was added to 5.0 g of phenol novolac resin TD2131 (manufactured by DIC Corporation) and 1.0 g of BMI70, and the solid content concentration was 5% by mass and the PGMEA concentration. was diluted with PGME so as to have a concentration of 30% by mass to prepare a composition 7 for forming a release layer.
• composition 8 for forming a release layer In 1 g of the reaction solution obtained in Synthesis Example 1, 0.04 g of PL-LI, 0.01 g of p-toluenesulfonic acid, and a non-fluorinated acrylic polymer UC-3510 ( 1.06 g of Toagosei Co., Ltd. and PGMEA were added and diluted with PGMEA so that the solid content concentration was 4% by mass and the PGMEA concentration was 30% by mass to prepare a release layer forming composition 8.
• release layer and resin substrate [Example 2-1] Using a spin coater (condition: rotation speed 1,000 rpm for about 30 seconds), the release layer forming composition 1 was applied onto a glass substrate (100 mm ⁇ 100 mm, the same applies hereinafter). The obtained coating film is heated at 100 ° C. for 2 minutes using a hot plate, and then heated at 230 ° C. for 10 minutes using a hot plate to form a release layer having a thickness of about 0.1 ⁇ m on a glass substrate. , A glass substrate with a release layer was obtained.
• the resin substrate forming composition F1 was applied onto the release layer (resin thin film) on the glass substrate using a spin coater (condition: rotation speed 200 rpm for about 15 seconds).
• the obtained coating film was heated at 80 ° C. for 2 minutes using a hot plate, and then heated at 230 ° C. for 30 minutes using a hot plate to form a resin substrate having a thickness of about 3 ⁇ m on the release layer.
• a resin substrate and a glass substrate with a release layer were obtained.
• the resin substrate showed a transmittance of 90% or more at 400 nm.
• Example 2-2 A release layer and a resin substrate were prepared in the same manner as in Example 2-1 except that the release layer forming composition 2 was used instead of the release layer forming composition 1, and the glass substrate and the resin with the release layer were prepared. Substrate ⁇ A glass substrate with a release layer was obtained.
• Example 2-3 A release layer and a resin substrate were prepared in the same manner as in Example 2-2 except that the resin substrate forming composition F2 was used instead of the resin substrate forming composition F1, and the glass substrate and the resin with the release layer were prepared.
• Substrate ⁇ A glass substrate with a release layer was obtained. Then, 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 90% or more at 400 nm.
• UV-2600 ultraviolet visible spectrophotometer
• Example 2-4 A release layer and a resin substrate were prepared in the same manner as in Example 2-1 except that the release layer forming composition 3 was used instead of the release layer forming composition 1, and the glass substrate and the resin with the release layer were prepared. Substrate ⁇ A glass substrate with a release layer was obtained.
• Example 2-5 A release layer and a resin substrate were prepared in the same manner as in Example 2-1 except that the release layer forming composition 4 was used instead of the release layer forming composition 1, and the glass substrate and the resin with the release layer were prepared. Substrate ⁇ A glass substrate with a release layer was obtained.
• Example 2-1 A release layer and a resin substrate were prepared in the same manner as in Example 2-1 except that the release layer forming composition 5 was used instead of the release layer forming composition 1, and the glass substrate and the resin with the release layer were prepared. Substrate ⁇ A glass substrate with a release layer was obtained.
• Example 2-2 A release layer and a resin substrate were prepared in the same manner as in Example 2-1 except that the release layer forming composition 6 was used instead of the release layer forming composition 1, and the glass substrate and the resin with the release layer were prepared. Substrate ⁇ A glass substrate with a release layer was obtained.
• Example 2-3 A release layer and a resin substrate were prepared in the same manner as in Example 2-1 except that the release layer forming composition 7 was used instead of the release layer forming composition 1, and the glass substrate and the resin with the release layer were prepared. Substrate ⁇ A glass substrate with a release layer was obtained.
• Example 2-4 A release layer and a resin substrate were prepared in the same manner as in Example 2-1 except that the release layer forming composition 8 was used instead of the release layer forming composition 1, and the glass substrate and the resin with the release layer were prepared. Substrate ⁇ A glass substrate with a release layer was obtained.
• ⁇ Change in peeling force of 0% or more and less than 10%
• ⁇ Change in peeling force of 10% or more and less than 30%
• ⁇ Change in peeling force of 30% or more and less than 50%
• ⁇ Change in peeling force of 50% or more-: Not measured

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