Composition for forming a release layer and release layer

Abstract

Provided is a composition for forming a release layer comprising a polymer including a repeating unit having a photosensitive group that undergoes photo-Fries rearrangement.

Description

Technical Field

[0001] The present invention relates to a composition for forming a release layer and a release layer.

Background Art

[0002] In recent years, in addition to the characteristics of thinning and lightening, electronic devices are required to have the function of being bendable. Therefore, instead of the conventional heavy, fragile, and non-bendable glass substrate, it is required to use a lightweight flexible plastic substrate.

[0003] In particular, as a new generation display, the development of an active matrix type full-color TFT display panel using a lightweight flexible plastic substrate (hereinafter also referred to as a resin substrate) is required. In addition, for touch panel type displays, materials corresponding to flexibility, such as transparent electrodes of touch panels and resin substrates used in combination with display panels, have been developed. As transparent electrodes, other transparent electrode materials have been proposed, such as transparent conductive polymers capable of bending, such as PEDOT, metal nanowires, and their mixed systems, instead of the conventionally used ITO (Patent Documents 1 to 4).

[0004] On the other hand, the base material of the touch panel film has also changed from glass to a sheet made of plastic such as polyethylene terephthalate (PET), polyimide, cycloolefin, acrylic, etc., and a transparent flexible touch screen panel having flexibility has been developed (Patent Documents 5 to 7). [[ID=二十一]] [[ID=二十二]]

[0005] [[ID=二十三]] Generally, flexible touchscreen panels are produced by creating a release (adhesive) layer on a support substrate such as a glass substrate, fabricating a device made of a resin substrate on top of it, and then peeling the device from the adhesive layer in order to ensure stable production (Patent Document 8). The device made of a resin substrate on top of this release layer must not be peeled off the support substrate during the process, but when peeling it off, a low peeling force is required. In particular, if it is peeled off the support substrate during the manufacturing process, it may lead to a significant decrease in yield. [Prior art documents] [Patent Documents]

[0006] [Patent Document 1] International Publication No. 2012 / 147235 [Patent Document 2] Japanese Patent Publication No. 2009-283410 [Patent Document 3] Special Publication No. 2010-507199 [Patent Document 4] Japanese Patent Publication No. 2009-205924 [Patent Document 5] International Publication No. 2017 / 002664 [Patent Document 6] International Publication No. 2016 / 160338 [Patent Document 7] Japanese Patent Publication No. 2015-166145 [Patent Document 8] Japanese Patent Publication No. 2016-531358 [Overview of the Initiative] [Problems that the invention aims to solve]

[0007] The present invention has been made in view of the above circumstances, and aims to provide a composition for forming a release layer that has high heat resistance and good release properties, and that can provide a release layer that can suppress unnecessary peeling during the process. [Means for solving the problem]

[0008] As a result of diligent research to achieve the above objective, the inventors have discovered that a release layer obtained from a release layer forming composition containing a polymer having repeating units having photosensitive groups that cause photofleece rearrangement has good release properties for resin substrates fabricated on the release layer, and that the adhesion to the resin substrate can be improved only in a predetermined area by exposure, thus completing the present invention.

[0009] In other words, the present invention provides the following composition for forming a release layer and a release layer. 1. (A) A composition for forming a release layer, comprising a polymer containing repeating units having photosensitive groups that cause photofleece rearrangement. 2. A composition for forming a release layer, wherein the repeating unit having a photosensitive group that causes the photofleece rearrangement is derived from a monomer represented by the following formula (a1) or (a2). [ka] (In the formula, Ar 1 is a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 2-biphenylyl group, a 3-biphenylyl group, or a 4-biphenylyl group, where some or all of the hydrogen atoms of these groups may be substituted with C1-C6 alkyl groups, C1-C6 alkoxy groups, chlorine atoms, or bromine atoms, but at least one of the ortho and para positions of the oxygen atom in the formula is a hydrogen atom; Ar 2 These are 1,2-phenylene group, 1,3-phenylene group, 1,4-phenylene group, 1,2-naphthylene group, 1,3-naphthylene group, 1,4-naphthylene group, 1,5-naphthylene group, 1,6-naphthylene group, 1,7-naphthylene group, 1,8-naphthylene group, 2,3-naphthylene group, 2,6-naphthylene group, 2,2'-biphenylylene group, 2,3'-biphenylylene group, The group is a 2,4'-biphenylylene group, a 3,3'-biphenylylene group, a 3,4'-biphenylylene group, or a 4,4'-biphenylylene group, where some or all of the hydrogen atoms of these groups may be substituted with C1-C6 alkyl groups, C1-C6 alkoxy groups, chlorine atoms, or bromine atoms, but at least one of the ortho and para positions of the oxygen atom in the formula is a hydrogen atom; R 1 is an alkyl group having 1 to 6 carbon atoms or a phenyl group; X 1 and X 2 each independently represents a single bond or an alkylene group having 1 to 20 carbon atoms, and one or more -CH2- of the alkylene group may be substituted with at least one group selected from -O-, -C(=O)-O-, and -O-C(=O)-; A 1 and A 2 each independently represents a radically polymerizable group containing a carbon-carbon double bond.) 3. The resin composition for forming a release layer according to 2, wherein the radically polymerizable group is represented by any one of the following formulas (A-1) to (A-4).

Chemical formula

Chemical formula

[0010] By using the release layer forming composition of the present invention, it is possible to reproducibly obtain a release layer that has good release properties for the resin substrate fabricated on the release layer and can enhance adhesion to the resin substrate only in a predetermined area by exposure. Furthermore, in the manufacturing process of flexible electronic devices, it is possible to suppress unnecessary peeling during manufacturing without damaging the resin substrate formed on the substrate or the circuits provided thereon, and to separate the resin substrate from the substrate together with the circuits when necessary. Therefore, the release layer forming composition of the present invention can contribute to speeding up the manufacturing process of flexible electronic devices equipped with a resin substrate and improving its yield. [Modes for carrying out the invention]

[0011] [Composition for forming a release layer] The release layer forming composition of the present invention comprises (A) a polymer containing repeating units having photosensitive groups that cause photofleece rearrangement.

[0012] [(A) Polymer] Component (A) in the release layer forming composition of the present invention is a polymer containing repeating units having a photosensitive group that undergoes a photofleece rearrangement.

[0013] The photo-Fries rearrangement is a process in which phenyl esters are irradiated with light to produce acylphenols, in which acyl groups are substituted at the ortho and para positions. Phenyl esters are a general term for esters formed between phenols and acids, specifically those formed between phenols and carboxylic acids. This rearrangement reaction is thought to proceed via a radical mechanism from an excited singlet state. [ka]

[0014] The release layer obtained from the polymer undergoes photo-Fleece rearrangement upon light irradiation, generating acylphenols. The generated acylphenols exhibit hydrophilicity and can undergo crosslinking reactions with resin substrates on the release layer, making it possible to control the release properties of the resin substrates on the release layer by light irradiation.

[0015] The monomer is preferably one represented by the following formula (a1) or (a2). [ka]

[0016] In equations (a1) and (a2), Ar 1 The group is a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 2-biphenylyl group, a 3-biphenylyl group, or a 4-biphenylyl group, and some or all of the hydrogen atoms of these groups may be substituted with C1-C6 alkyl groups, C1-C6 alkoxy groups, chlorine atoms, or bromine atoms, but at least one of the ortho and para positions of the oxygen atom in the formula is a hydrogen atom.

[0017] In equations (a1) and (a2), Ar 2 These are 1,2-phenylene group, 1,3-phenylene group, 1,4-phenylene group, 1,2-naphthylene group, 1,3-naphthylene group, 1,4-naphthylene group, 1,5-naphthylene group, 1,6-naphthylene group, 1,7-naphthylene group, 1,8-naphthylene group, 2,3-naphthylene group, 2,6-naphthylene group, 2,2'-biphenylylene group, 2,3'-biphenylylene group, The group is a 2,4'-biphenylylene group, a 3,3'-biphenylylene group, a 3,4'-biphenylylene group, or a 4,4'-biphenylylene group, and some or all of the hydrogen atoms of these groups may be substituted with C1-C6 alkyl groups, C1-C6 alkoxy groups, chlorine atoms, or bromine atoms, but at least one of the ortho and para positions of the oxygen atom in the formula is a hydrogen atom.

[0018] In equations (a1) and (a2), R 1 This is an alkyl group or phenyl group having 1 to 6 carbon atoms.

[0019] In equations (a1) and (a2), X 1 and X 2 Each of these is independently a single bond or an alkylene group having 1 to 20 carbon atoms, and one or more of the -CH2- groups of the alkylene group may be substituted with at least one group selected from -O-, -C(=O)-O-, and -OC(=O)-.

[0020] The C1-C6 alkyl group may be linear, branched, or cyclic. Specific examples include methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, cyclobutyl, n-pentyl, cyclopentyl, n-hexyl, and cyclohexyl groups.

[0021] The alkoxy group having 1 to 6 carbon atoms may be linear, branched, or cyclic. Specific examples include methoxy, ethoxy, n-propyloxy, isopropyloxy, cyclopropyloxy, n-butyloxy, isobutyloxy, sec-butyloxy, tert-butyloxy, cyclobutyloxy, n-pentyloxy, cyclopentyloxy, n-hexyloxy, and cyclohexyloxy groups.

[0022] The alkylene group having 1 to 20 carbon atoms may be linear, branched, or cyclic. Specific examples include methylene group, methylmethylene group, dimethylmethylene group, ethylene group, trimethylene group, propylene group, tetramethylene group, pentamethylene group, hexamethylene group, and the like.

[0023] Ar 1 As such, unsubstituted phenyl groups, 1-naphthyl groups, 2-naphthyl groups, 3-biphenylyl groups, and 4-biphenylyl groups are preferred. 2 As such, unsubstituted 1,4-phenylene groups and 4,4'-biphenylene groups are preferred. 1 and X 2 A single bond is preferred.

[0024] In equations (a1) and (a2), A 1 and A 2 Each of these is independently a radical polymerizable group containing a carbon-carbon double bond. The radical polymerizable group is preferably one represented by any of the following formulas (A-1) to (A-4). [ka] (R A These are, independently, a hydrogen atom or a methyl group.

[0025] A 1 and A 2 Preferably, it is represented by formula (A-1) or (A-2).

[0026] Specific examples of monomers represented by formula (a1) include, but are not limited to, those represented by the following formulas (a1-1) to (a1-5). Note that in the following formulas, A 1 and X 1 This is the same as described above. [ka]

[0027] Preferred specific examples of the monomer represented by formula (a1) include, but are not limited to, those represented by the following formulas (a1-1') to (a1-5'). [ka]

[0028] Specific examples of monomers represented by formula (a2) include, but are not limited to, those represented by the following formulas (a2-1) to (a2-4). Note that in the following formulas, A 2 and X 2 This is the same as described above. [ka]

[0029] Preferred specific examples of monomers represented by formula (a2) include, but are not limited to, those represented by the following formulas (a2-1') to (a2-4'). [ka]

[0030] In the polymer of component (A), the content of repeating units derived from the monomer represented by formula (a1) and / or (a2) may be 100 mol%, but is preferably 10 to 60 mol%, and more preferably 15 to 50 mol% of the total repeating units.

[0031] The polymer of component (A) preferably further comprises repeating units derived from the monomer represented by the following formula (b) and repeating units derived from the monomer represented by the following formula (c). [ka]

[0032] In equations (b) and (c), R A Each of these is independently either a hydrogen atom or a methyl group. B R is a branched alkyl group having 3 or 4 carbon atoms, in which at least one hydrogen atom is substituted with a fluorine atom. C These are hydroxyalkyl groups with 2 to 10 carbon atoms.

[0033] Examples of the branched alkyl group having 3 or 4 carbon atoms include isopropyl, isobutyl, sec-butyl, and tert-butyl groups. B Preferably, these branched alkyl groups have at least one hydrogen atom substituted with a fluorine atom. Specific examples include 1,1,1-trifluoroisopropyl group, 1,1,1,3,3,3-hexafluoroisopropyl group, and nonafluoro-tert-butyl group.

[0034] Examples of the hydroxyalkyl groups having 2 to 10 carbon atoms include 1-hydroxyethyl group, 1-hydroxypropyl group, 2-hydroxypropyl group, 2-hydroxybutyl group, 2-hydroxyhexyl group, 2-hydroxyoctyl group, 2-hydroxydecyl group, 1-hydroxy-1-methylethyl group, and 2-hydroxy-2-methylpropyl group.

[0035] Examples of monomers represented by formula (b) include, but are not limited to, those represented by the following formulas (b-1) to (b-3). Note that in the following formulas, R A This is the same as described above. [ka]

[0036] Examples of monomers represented by formula (c) include, but are not limited to, those represented by the following formulas (c-1) to (c-4). Note that in the following formulas, R A This is the same as described above. [ka]

[0037] If the polymer of component (A) contains repeating units derived from the monomer represented by formula (b) and repeating units derived from the monomer represented by formula (c) below, the content of repeating units derived from the monomer represented by (b) is preferably 5 to 60 mol%, and more preferably 10 to 50 mol%, of the total repeating units. The content of repeating units derived from the monomer represented by formula (c) is preferably 5 to 60 mol%, and more preferably 10 to 50 mol%, of the total repeating units.

[0038] The polymer of component (A) may contain repeating units derived from monomers other than those described above (hereinafter also referred to as "other monomers"), as long as the effects of the present invention are not impaired. Examples of other monomers include acrylic acid ester compounds, methacrylic acid ester compounds, maleimide compounds, acrylamide compounds, acrylonitrile, maleic anhydride, styrene compounds, vinyl compounds, and the like.

[0039] Specific examples of the aforementioned acrylic acid ester compounds include methyl acrylate, ethyl acrylate, isopropyl acrylate, benzyl acrylate, naphthyl acrylate, anthyl acrylate, anthyl methyl acrylate, phenyl acrylate, 2,2,2-trifluoroethyl acrylate, tert-butyl acrylate, cyclohexyl acrylate, isobornyl acrylate, 2-methoxyethyl acrylate, methoxytriethylene glycol acrylate, 2-ethoxyethyl acrylate, tetrahydrofurfuryl acrylate, 3-methoxybutyl acrylate, 2-methyl-2-adamantyl acrylate, 2-propyl-2-adamantyl acrylate, 8-methyl-8-tricyclo[5.2.1.0(2,6)]decyl acrylate, and 8-ethyl-8-tricyclo[5.2.1.0(2,6)]decyl acrylate.

[0040] Specific examples of the methacrylate ester compounds mentioned above include methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, benzyl methacrylate, naphthyl methacrylate, anthlyl methacrylate, anthlyl methyl methacrylate, phenyl methacrylate, 2,2,2-trifluoroethyl methacrylate, tert-butyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, 2-methoxyethyl methacrylate, methoxytriethylene glycol methacrylate, 2-ethoxyethyl methacrylate, tetrahydrofurfuryl methacrylate, 3-methoxybutyl methacrylate, 2-methyl-2-adamantyl methacrylate, 2-propyl-2-adamantyl methacrylate, 8-methyl-8-tricyclo[5.2.1.0(2,6)]decyl methacrylate, and 8-ethyl-8-tricyclo[5.2.1.0(2,6)]decyl methacrylate.

[0041] Specific examples of the vinyl compound include vinyl ether, methyl vinyl ether, benzyl vinyl ether, 2-hydroxyethyl vinyl ether, phenyl vinyl ether, and propyl vinyl ether.

[0042] Specific examples of the aforementioned styrene compounds include styrene, 4-methylstyrene, 4-chlorostyrene, and 4-bromostyrene.

[0043] Specific examples of the maleimide compounds mentioned above include maleimide, N-methylmaleimide, N-phenylmaleimide, and N-cyclohexylmaleimide.

[0044] The weight-average molecular weight (Mw) of the polymer of component (A) is preferably 1,000 to 20,000, and more preferably 2,000 to 10,000. Furthermore, its dispersion (Mw / Mn) is preferably 1.0 to 3.0, and more preferably 1.0 to 2.5. Note that Mw is a polystyrene-converted value measured by gel permeation chromatography (GPC).

[0045] The method for synthesizing the polymer is not particularly limited, but one example is to carry out a polymerization reaction at a temperature of 50 to 110°C in a solvent containing the monomer and polymerization initiator mentioned above. The solvent used is not particularly limited as long as it dissolves the monomer and polymerization initiator. Specific examples include those exemplified as the solvent for component (E) described later.

[0046] The polymer obtained in this way is usually in the form of a solution dissolved in a solvent and can be used as is as a solution of component (A) in the present invention.

[0047] Furthermore, the polymer powder can be recovered by adding the polymer solution to hexane, methanol, water, etc., under stirring to reprecipitate, filtering the resulting precipitate, washing it, and then drying it at room temperature or under reduced pressure. This operation removes polymerization initiators and unreacted monomers coexisting with the polymer, resulting in purified polymer powder. If sufficient purification cannot be achieved in a single operation, the obtained powder can be redissolved in a solvent and the above operation can be repeated. The polymer powder may be used as component (A) as is, or the powder may be redissolved in a solvent, for example, as described later, and used in solution form.

[0048] In the release layer forming composition of the present invention, the polymer of component (A) may be used alone or in combination of two or more types.

[0049] [(B) Resins having hydroxyl or carboxyl groups] The release layer forming composition of the present invention may optionally contain a resin having a hydroxyl group or a carboxyl group as component (B). While not particularly limited, such resins are preferably polyureas having hydroxyl groups, acrylic polymers having hydroxyl or carboxyl groups, polyesters having hydroxyl groups, or cellulose or derivatives thereof having a hydroxyalkyl group.

[0050] The polyurea having the hydroxyl group is preferably one that contains a repeating unit represented by the following formula (1). [ka]

[0051] In formula (1), A 1 , A 2 , A 3 , A 4 , A 5 and A 6 These are, independently, a hydrogen atom, a methyl group, or an ethyl group, but from the viewpoint of exfoliation and productivity, A 1 ~A 6 It is preferable that all of them are hydrogen atoms.

[0052] In formula (1), X 1 This is a group represented by the following formulas (X1), (X2), (X3), or (X4). [ka] (In the formula, * represents a bond with the carbonyl group. ** represents a bond with the nitrogen atom.)

[0053] In equations (X1) and (X2), R 1 and R 2 Each of these is independently a hydrogen atom, a C1-C6 alkyl group, a C3-C6 alkenyl group, a benzyl group, or a phenyl group. The phenyl group may be substituted with at least one group selected from the group consisting of a C1-C6 alkyl group, a halogen atom, a C1-C6 alkoxy group, a nitro group, a cyano group, a hydroxyl group, and a C1-C6 alkylthio group. Also, R 1 and R 2 These atoms may bond with each other to form a ring with 3 to 6 carbon atoms, together with the carbon atoms to which they are bonded.

[0054] In formula (X3), R 3This is 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. The phenyl group may be substituted with at least one group selected from the group consisting of alkyl groups having 1 to 6 carbon atoms, halogen atoms, alkoxy groups having 1 to 6 carbon atoms, nitro groups, cyano groups, hydroxyl groups, and alkylthio groups having 1 to 6 carbon atoms.

[0055] In formula (1), Q 1 This is a group represented by the following formula (Q1) or (Q2). [ka] (In the formula, * represents a coupling.)

[0056] In formula (Q1), X 2 is a base represented by formula (X1), formula (X2), or formula (X4). In formula (Q1), for example, X 2 If the base is represented by equation (X2), its structure is given by the following equation (Q1-1). [ka] (In the formula, R 1 and R 2 (The same as above. * indicates a coupling.)

[0057] In formula (Q2), Q 2 This is an alkylene group, phenylene group, naphthylene group, or anthrylene group having 1 to 10 carbon atoms. The phenylene group, naphthylene group, and anthrylene group may be substituted with at least one group selected from the group consisting of alkyl groups having 1 to 6 carbon atoms, halogen atoms, alkoxy groups having 1 to 6 carbon atoms, nitro groups, cyano groups, hydroxyl groups, and alkylthio groups having 1 to 6 carbon atoms. Also, Q 2When the group is a phenylene group, naphthylene group, or anthrylene group, the positions of their bonds are not particularly limited. That is, for example, the phenylene group may be bonded at positions 1 and 2, 1 and 3, or 1 and 4; the naphthylene group may be bonded at positions 1 and 2, 1 and 4, 1 and 5, or 2 and 3; the anthrylene group may be bonded at positions 1 and 2, 1 and 4, or 9 and 10, etc., and any of these may be acceptable. 1 and n 2 Each of these is independently either 0 or 1.

[0058] The C1-C6 alkyl group may be linear, branched, or cyclic, and specific examples include methyl, ethyl, isopropyl, n-butyl, and cyclohexyl groups. The C3-C6 alkenyl group may be linear, branched, or cyclic, and examples include 2-propenyl and 3-butenyl groups.

[0059] The alkoxy group having 1 to 6 carbon atoms may be linear, branched, or cyclic, and specific examples include methoxy, ethoxy, isopropoxy, n-pentyloxy, and cyclohexyloxy groups. The alkylthio group having 1 to 6 carbon atoms may be linear, branched, or cyclic, and specific examples include methylthio, ethylthio, isopropylthio, n-pentylthio, and cyclohexylthio groups. The halogen atom may be a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. Also, R 1 and R 2 Examples of rings with 3 to 6 carbon atoms formed by the bonding of these atoms include cyclobutane rings, cyclopentane rings, and cyclohexane rings.

[0060] The alkylene group having 1 to 10 carbon atoms may be linear, branched, or cyclic. Specific examples include methylene, ethylene, propylene, pentamethylene, cyclohexylene, and 2-methylpropylene groups.

[0061] Note that in equation (1), X 1 If the group is represented by formula (X2), its structure will be represented by the following formula (1A), and X 1 If the group is represented by formula (X3), its structure will be represented by the following formula (1B). Also, in formula (X3), R 3 However, a 2-propenyl group is preferred. [ka] (In the formula, A 1 ~A 6 , R 1 ~R 3 and Q 1 (This is the same as above.)

[0062] In formula (1), Q 1 From the viewpoint of the heat resistance of the polyurea, it is preferable that it contains a cyclic structure. That is, Q 1 However, the group represented by formula (Q1), or the group represented by formula (Q2), and Q 2 It is preferable that the group is a cyclic alkylene group, a phenylene group, a naphthylene group, or an anthrylene group, and more preferably a group represented by formula (Q1).

[0063] The repeating unit represented by formula (1) is preferably one represented by the following formulas (1-1) to (1-19). In the following formulas, Me is a methyl group and Et is an ethyl group. [ka]

[0064] [ka]

[0065] [ka]

[0066] [ka]

[0067] [ka]

[0068] [ka]

[0069] [ka]

[0070] The aforementioned polyurea can be synthesized, for example, by referring to International Publication No. 2005 / 098542.

[0071] As the acrylic polymer having a hydroxyl group or carboxyl group, you can use a homopolymer of acrylic acid esters, a homopolymer of methacrylic acid esters, copolymers thereof, and copolymers thereof with monomers having unsaturated double bonds such as styrene.

[0072] A preferred example of the acrylic polymer is an acrylic polymer having polyethylene glycol ester groups or hydroxyalkyl ester groups having 2 to 6 carbon atoms. Such an acrylic polymer can be any acrylic polymer having either of these groups, and there are no particular limitations on the backbone (other repeating units) of the main chain or the type of side chains constituting the acrylic polymer.

[0073] The acrylic polymer having polyethylene glycol ester groups or hydroxyalkyl ester groups having 2 to 6 carbon atoms is preferably one that contains repeating units represented by the following formula (2).

[0074] [ka]

[0075] In formula (2), R 11 R is a hydrogen atom or a methyl group. 12 is -(CH2CH2O) n -It is an H group or a hydroxyalkyl group having 2 to 6 carbon atoms. n is an integer from 2 to 30, preferably an integer from 2 to 10.

[0076] Examples of the hydroxyalkyl groups having 2 to 6 carbon atoms include 1-hydroxyethyl group, 2-hydroxyethyl group, 1-hydroxypropyl group, 2-hydroxypropyl group, 3-hydroxypropyl group, 1-hydroxybutyl group, 2-hydroxybutyl group, 3-hydroxybutyl group, 4-hydroxybutyl group, and 2,3-dihydroxypropyl group.

[0077] Furthermore, the acrylic polymer may also contain repeating units other than those represented by formula (2), specifically repeating units derived from monomers that do not have polyethylene glycol ester groups and hydroxyalkyl ester groups having 2 to 6 carbon atoms, as long as the effects of the present invention are not impaired.

[0078] The method for producing the acrylic polymer is not particularly limited, but for example, it is a method in which a monomer having at least one of polyethylene glycol groups and a hydroxyalkyl group having 2 to 6 carbon atoms is polymerized in a solution in which a polymerization initiator is dissolved in a solvent at a temperature of 50 to 110°C, and optionally a monomer that does not have polyethylene glycol ester groups and a hydroxyalkyl ester group having 2 to 6 carbon atoms is polymerized. The solvent used is not particularly limited as long as it can dissolve the monomer, polymerization initiator, etc.

[0079] The monomer having the polyethylene glycol ester group is H-(OCH2CH2) n Examples include monoacrylates or monomethacrylates of -OH (where n is the same as above). Examples of monomers having a hydroxyalkyl group with 2 to 6 carbon atoms include 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl methacrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, glycerin monoacrylate, glycerin monomethacrylate, and the like.

[0080] Examples of monomers that do not have polyethylene glycol ester groups and carbon 2-6 hydroxyalkyl ester groups include carboxylic acid compounds such as acrylic acid and methacrylic acid; acrylic acid ester compounds such as methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate, isobutyl acrylate, t-butyl acrylate, phenyl acrylate, and 4-hydroxyphenyl acrylate; methacrylic acid ester compounds such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, butyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, phenyl methacrylate, and 4-hydroxyphenyl methacrylate; maleimide compounds such as maleimide, N-methyl maleimide, N-phenyl maleimide, N-(4-hydroxyphenyl) maleimide, and N-cyclohexyl maleimide; acrylamide compounds; methacrylamide compounds; acrylonitrile; maleic anhydride; styrene compounds; and vinyl compounds.

[0081] The acrylic polymer obtained by the above method is usually in the form of a solution dissolved in a solvent.

[0082] Preferred examples of the acrylic polymer include polymers obtained by polymerizing hydroxyalkyl ester monomers such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, glycerin monoacrylate, and glycerin monomethacrylate; and acrylic polymers having hydroxyalkyl groups in their side chains, such as polymers obtained by copolymerizing the hydroxyalkyl ester monomers with one or more monomers selected from the group consisting of polyethylene glycol ester groups and monomers having 2 to 6 carbon atoms that do not have a hydroxyalkyl ester group.

[0083] The polyester having the hydroxyl group is not particularly limited, but it is preferable that it has an aromatic group or an alicyclic group in its main chain. As such a polyester, a polyester obtained by reacting a compound having two or more epoxy moieties with a compound having two carboxyl groups is preferred.

[0084] Examples of compounds having two or more epoxy moieties include bisphenol diglycidyl ethers such as bisphenol F diglycidyl ether, bisphenol A diglycidyl ether, bisphenol B diglycidyl ether, bisphenol AD ​​diglycidyl ether, bisphenol S diglycidyl ether, tetrachlorobisphenol A diglycidyl ether, catechin diglycidyl ether, resorcinol diglycidyl ether, hydroquinone diglycidyl ether, 1,5-dihydroxynaphthalene diglycidyl ether, dihydroxybiphenyl diglycidyl ether, octachloro-4,4'-dihydroxybiphenyl diglycidyl ether, tetramethylbiphenyl diglycidyl ether, 9,9'-bis(4-hydroxyphenyl)flourangorange glycidyl ether, 9,9'-bis(4-hydroxyphenyl)flourangorange glycidyl ether, and 9,9'-bis(6-hydroxy-2-naphthyl)flourangorange glycidyl ether; ethylene glycol diglycidyl ether, and propylene Aliphatic diol diglycidyl ethers such as glycol diglycidyl ether, tetramethylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether; cyclohexanediol diglycidyl ether, cyclohexanedimethanol diglycidyl ether, dicyclopentadienediol diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, hydrogenated bisphenol A diglycidyl ether Alicyclic diol diglycidyl ethers such as lysidyl ether, hydrogenated bisphenol B diglycidyl ether, and hydrogenated bisphenol S diglycidyl ether; aromatic diglycidyl esters such as diglycidyl phthalate, diglycidyl isophthalate, and diglycidyl terephthalate; alicyclic diglycidyl esters such as bisglycidyl oxalate, bisglycidyl adipic acid, bisglycidyl pimelate, and bisglycidyl 2-ethyl-3-propyl-1,5-pentanedioate;Examples include alicyclic dicarboxylic acid diester diepoxides such as bis(3,4-epoxycyclohexylmethyl) oxalate, bis(3,4-epoxycyclohexylmethyl) adipate, bis(3,4-epoxy-6-methylcyclohexylmethyl) adipate, bis(3,4-epoxycyclohexylmethyl) pimelate, and bis(3,4-epoxycyclohexylmethyl) 2-ethyl-3-propyl-1,5-pentanedioate; and alicyclic dioxides such as vinylcyclohexene dioxide, limonene dioxide, dicyclopentadiene dioxide, Epocalic® THI-DE, DE-102, DE-103 (manufactured by ENEOS Corporation), 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, and 2,2-bis(3,4-epoxycyclohexyl)propane. These compounds may be used individually or in combination of two or more.

[0085] Compounds having two carboxyl groups include terephthalic acid, isophthalic acid, diphenic acid, 2-methylterephthalic acid, 2-hydroxyterephthalic acid, 2,5-dimethylterephthalic acid, 5-methylisophthalic acid, 5-hydroxyisophthalic acid, 2,6-naphthalenedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, and 1,4-cyclohexanedicarboxylic acid. These compounds may be used individually or in combination of two or more.

[0086] The method for synthesizing the polyester is not particularly limited, but one example is a polymerization reaction carried out at a temperature of 50 to 150°C in a solvent containing the ester compound, a carboxyl group-containing compound, and a catalyst. The solvent used is not particularly limited as long as it dissolves the compound, polymerization initiator, etc. The polyester obtained by the above method is usually in the form of a solution dissolved in the solvent.

[0087] The aforementioned polyester is preferably one that contains repeating units represented by the following formula (3). [ka]

[0088] In formula (3), Y 1 and Z 1 These are, independently, divalent groups having either an aromatic ring or an alicyclic ring.

[0089] Y 1 A group represented by the following formula (Y1-1) is preferred. [ka] (In the formula, * represents a coupling.)

[0090] In formula (Y1-1), L 1 These are, independently, ether bonds or ester bonds. 2 Each of these is independently a divalent cyclic unsaturated hydrocarbon group having 3 to 10 carbon atoms or a divalent cyclic saturated hydrocarbon group having 3 to 10 carbon atoms. 21 p is a single bond, an ether bond, a carbonyl group, a sulfonyl group, a divalent saturated hydrocarbon group having 1 to 30 carbon atoms, a divalent unsaturated hydrocarbon group having 2 to 30 carbon atoms, or a divalent saturated hydrocarbon group having 1 to 30 carbon atoms substituted with a fluorine atom. p is 0, 1, or 2.

[0091] Y 2 Preferably, the C4-C16 divalent cyclic unsaturated hydrocarbon group or the C4-C16 divalent cyclic saturated hydrocarbon group is preferred, and more preferably, the C4-C8 divalent cyclic unsaturated hydrocarbon group or the C4-C8 divalent cyclic saturated hydrocarbon group is preferred. Also, Y 2 Some or all of the hydrogen atoms contained in may be substituted with aliphatic groups, and some of these substituents may bond to each other to form a 4-6 membered ring.

[0092] Y 2 Specific examples include, but are not limited to, the groups represented by the following formulas (Y2-1) to (Y2-12). [ka] (In the formula, * represents a coupling.)

[0093] Z 1 Preferably, the group is an arylene group having 6 to 20 carbon atoms or a divalent cyclic saturated hydrocarbon group having 3 to 20 carbon atoms. The arylene group or divalent cyclic saturated hydrocarbon group may be substituted with a hydroxyl group, a methyl group, or the like.

[0094] Z 1 Specific examples include, but are not limited to, the bases represented by the following formulas (Z1-1) to (Z1-4). [ka] (In the formula, * represents a coupling.)

[0095] The aforementioned polyester may also have repeating units represented by the following formula (4). [ka]

[0096] In formula (4), Z 1 The same applies as described above. The Cy ring is a tetravalent cyclic saturated hydrocarbon group having 4 to 20 carbon atoms or a tetravalent group represented by the following formula (Cy-1). [ka]

[0097] In formula (Cy-1), Cy' is a trivalent cyclic saturated hydrocarbon group having 4 to 20 carbon atoms. 31 *1 is a divalent saturated hydrocarbon group having 1 to 20 carbon atoms or a divalent unsaturated hydrocarbon group having 2 to 20 carbon atoms, and may contain ester bonds, etc. *1 and *2 are bonding sites, and one of the two *1 and *2 is bonded to a hydroxyl group.

[0098] The tetravalent cyclic saturated hydrocarbon group and the trivalent cyclic saturated hydrocarbon group may be monocyclic or polycyclic. In the case of polycyclic, they may be fused rings, bridged rings, spiro rings, or contain multiple of these ring structures.

[0099] Specific examples of groups represented by Cy include the groups represented by the following formulas (Cy-2) to (Cy-8). [ka] (In the formula, *1 and *2 are bonding sites, and one of the two *1 and *2 in each structural formula is bonded to a hydroxyl group.)

[0100] Examples of cellulose or derivatives having a hydroxyalkyl group include hydroxyalkylcelluloses such as hydroxyethylcellulose and hydroxypropylcellulose, hydroxyalkylalkylcelluloses such as hydroxyethylmethylcellulose, hydroxypropylmethylcellulose, and hydroxyethylethylcellulose, and derivatives thereof. Of these, hydroxyalkylcelluloses and their derivatives are preferred, and hydroxyethylcellulose, hydroxypropylcellulose, and their derivatives are more preferred. The cellulose or derivative having a hydroxyalkyl group may be used alone or in combination of two or more.

[0101] The weight-average molecular weight (Mw) of component (B) is not particularly limited, but is preferably 1,000 to 500,000, more preferably 3,000 to 400,000, and even more preferably 5,000 to 300,000.

[0102] When the release layer forming composition of the present invention contains component (B), its content is preferably 0.1 to 100 parts by mass, and more preferably 0.5 to 50 parts by mass, per 1 part by mass of component (A). If the content of component (B) is within the above range, a release layer resin composition can be obtained that has high heat resistance, moderate release properties, and excellent stability after film formation. Component (B) may be used alone or in combination of two or more types.

[0103] [(C) Crosslinking agent] The composition for forming a release layer of the present invention may contain a crosslinking agent as component (C) if necessary. The crosslinking agent is selected from compounds having a nitrogen atom substituted with a hydroxyalkyl group and / or an alkoxymethyl group.

[0104] As the crosslinking agent, a compound represented by any of the following formulas (C-1) to (C-5) is preferable.

Chemical formula

[0105] In formulas (C-1) to (C-5), R 101 ~R 116 are each independently an alkyl group having 1 to 6 carbon atoms. R B is a hydrogen atom or a methyl group.

[0106] Specific examples of the crosslinking agent include nitrogen-containing compounds such as hexamethoxymethylmelamine, tetramethoxymethylbenzoguanamine, 1,3,4,6-tetrakis(methoxymethyl) glycoluril, 1,3,4,6-tetrakis(butoxymethyl) glycoluril, and 1,3,4,6-tetrakis(hydroxymethyl) glycoluril.

[0107] In addition, commercially available nitrogen-containing compounds such as methoxymethyl type melamine compounds (trade names Cymel (registered trademark) 300, Cymel 301, Cymel 303, Cymel 350) manufactured by Allnex, butoxymethyl type melamine compounds (trade names Mycote (registered trademark) 506, Mycote 508), glycoluril compounds (trade names Cymel 1170, Powderlink 1174), methylated urea resins (trade name UFR65), butylated urea resins (trade names UFR300, U-VAN10S60, U-VAN10R, U-VAN11HV), and urea / formaldehyde resins (trade names Beckamine (registered trademark) J-300S, Beckamine P-955, Beckamine N) manufactured by DIC Corporation can be mentioned.

[0108] Furthermore, polymers produced using (meth)acrylamide compounds substituted with hydroxymethyl or alkoxymethyl groups, such as N-hydroxymethyl(meth)acrylamide, N-methoxymethyl(meth)acrylamide, N-ethoxymethyl(meth)acrylamide, and N-butoxymethyl(meth)acrylamide, can be used as crosslinking agents. Examples of such polymers include poly(N-butoxymethyl(meth)acrylamide), copolymers of N-butoxymethyl(meth)acrylamide and styrene, copolymers of N-hydroxymethyl(meth)acrylamide and methyl(meth)acrylate, copolymers of N-ethoxymethylmethacrylamide and benzyl methacrylate, and copolymers of N-butoxymethyl(meth)acrylamide, benzyl(meth)acrylate, and 2-hydroxypropyl(meth)acrylate.

[0109] More preferably used as the crosslinking agent are hexamethoxymethylmelamine, tetramethoxymethylbenzoguanamine, 1,3,4,6-tetrakis(methoxymethyl)glycoluryl (POWDERLINK 1174), 1,3,4,6-tetrakis(butoxymethyl)glycoluryl, and 1,3,4,6-tetrakis(hydroxymethyl)glycoluryl.

[0110] These crosslinking agents can undergo crosslinking reactions through self-condensation. They can also undergo crosslinking reactions with hydroxyl groups or carboxyl groups in the resin of component (A) or (B). As a result of such crosslinking reactions, the resulting release layer becomes strong and has low solubility in organic solvents.

[0111] If the release layer forming composition of the present invention contains component (C), the content of component (C) is preferably 1 to 1,000 parts by mass, and more preferably 2 to 800 parts by mass, per 100 parts by mass of component (A) if component (B) is not included. If component (B) is included, the content is preferably 5 to 200 parts by mass, and more preferably 10 to 100 parts by mass, per 100 parts by mass of the total of components (A) and (B). If the content of component (C) is within the above range, a release layer resin composition having high heat resistance and appropriate release properties, and excellent stability after film formation can be obtained. The crosslinking agent (C) may be used alone or in combination of two or more types.

[0112] [(D) Crosslinking catalyst] The release layer forming composition of the present invention may contain a crosslinking catalyst as component (D). Examples of the crosslinking catalyst include sulfonic acid compounds, carboxylic acid compounds, and salts thereof.

[0113] Specific examples of the sulfonic acid compounds include p-toluenesulfonic acid, trifluoromethanesulfonic acid, pyridinium-p-toluenesulfonate, salicylic acid, camphorsulfonic acid, sulfosalicylic acid, 4-chlorobenzenesulfonic acid, 4-hydroxybenzenesulfonic acid, benzenedisulfonic acid, 1-naphthalenesulfonic acid, and pyridinium-1-naphthalenesulfonic acid. Specific examples of the carboxylic acid compounds include salicylic acid, sulfosalicylic acid, citric acid, benzoic acid, and hydroxybenzoic acid.

[0114] Examples of salts of the acid compound include pyridinium salts, isopropanolamine salts, and N-methylmorpholine salts of the acid. Specific examples of salts of the sulfonic acid compound include p-toluenesulfonate pyridinium, 1-naphthalenesulfonate pyridinium, isopropanolamine p-toluenesulfonate, and N-methylmorpholine p-toluenesulfonate. Specific examples of salts of the carboxylic acid compound include isopropanolamine salicylate and isopropanolamine sulfosalicylic acid.

[0115] If the release layer forming composition of the present invention contains component (D), its content is preferably 0.01 to 100 parts by mass, and more preferably 0.1 to 80 parts by mass, per 100 parts by mass of component (A) if component (B) is not included. If component (B) is included, its content is preferably 0.01 to 15 parts by mass, and more preferably 0.1 to 10 parts by mass, per 100 parts by mass of the total of components (A) and (B). If the content of component (D) is within the above range, a release layer resin composition that provides a release layer having high heat resistance and appropriate release properties can be obtained. The crosslinking catalyst (D) may be used alone or in combination of two or more types.

[0116] [(E) Solvent] The release layer forming composition of the present invention may contain a solvent as component (E). The solvent is not particularly limited as long as it can dissolve component (A) and components (B), (C), (D) and / or other additives described later as needed, but in the present invention, glycol ether solvents having 3 to 20 carbon atoms, ester solvents having 3 to 20 carbon atoms, ketone solvents having 3 to 20 carbon atoms, and amide solvents are preferred.

[0117] Specific examples of the glycol ether solvent include propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether, and propylene glycol monopropyl ether. Specific examples of the ester solvent include ethyl lactate, γ-butyrolactone, methyl 2-hydroxyisobutyrate, and ethyl 2-hydroxyisobutyrate. Specific examples of the ketone solvent include methyl ethyl ketone, cyclohexanone, cyclopentanone, and benzophenone. Specific examples of the amide solvent include N-methylpyrrolidone, N,N-dimethylacetamide, and 3-methoxy-N,N-dimethylpropanamide.

[0118] (E) The amount of component (E) is preferably such that the solid content concentration in the release layer forming composition of the present invention is 0.1 to 40% by mass, more preferably 0.5 to 20% by mass, and even more preferably 0.5 to 10% by mass. The solid content refers to all components of the release layer forming composition other than the solvent. (E) The solvent may be used alone or as a mixture of two or more types.

[0119] [Other ingredients] The release layer forming composition of the present invention may optionally contain a surfactant. By adding a surfactant, the coatability of the release layer forming composition on the substrate can be improved. As the surfactant, known surfactants such as nonionic surfactants, fluorinated surfactants, and silicone surfactants can be used.

[0120] Specific examples of nonionic surfactants include, for example, polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, and polyoxyethylene oleyl ether; polyoxyethylene alkylaryl ethers such as polyoxyethylene octylphenyl ether and polyoxyethylene nonylphenyl ether; polyoxyethylene-polyoxypropylene block copolymers; sorbitan fatty acid esters such as sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, and sorbitan tristearate; and polyoxyethylene sorbitan fatty acid esters such as polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, and polyoxyethylene sorbitan tristearate.

[0121] Specific examples of the aforementioned fluorine-based surfactants include F-Top® EF301, EF303, EF352 (manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd.), Megafac® F171, F173, F554, F559, F563, R-30, R-40, R-40-LM, DS-21 (manufactured by DIC Corporation), FLUORAD® FC430, FC431 (manufactured by 3M Company), Asahiguard® AG710, Surflon® S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by AGC Inc.), and others.

[0122] Furthermore, specific examples of silicone-based surfactants include organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.).

[0123] If the release layer forming composition of the present invention contains a surfactant, its content is preferably 0.0001 to 1 part by mass, and more preferably 0.001 to 0.5 parts by mass, per 100 parts by mass of component (A). The surfactant may be used alone or in combination of two or more types.

[0124] Furthermore, the peel-off layer forming composition of the embodiment of the present invention may contain other additives such as silane coupling agents, rheology modifiers, pigments, dyes, preservative stabilizers, defoaming agents, antioxidants, etc., as long as the effects of the present invention are not impaired.

[0125] [Method for preparing a composition for forming a release layer] The method for preparing the release layer-forming composition of the present invention is not particularly limited. For example, a method may be used in which a solution of component (A) dissolved in a solvent is mixed with components (B), (C), and / or other components in predetermined proportions, simultaneously or in any order, to obtain a homogeneous solution. It is preferable to filter the prepared release layer-forming composition solution using a filter with a pore size of about 0.2 μm before use.

[0126] The viscosity of the release layer forming composition of the present invention is set appropriately considering the thickness of the release layer to be produced, etc. In particular, when the aim is to obtain a film with a thickness of about 0.01 to 50 μm with good reproducibility, the viscosity is usually preferably about 1 to 5,000 mPa·s at 25°C, and more preferably about 1 to 2,000 mPa·s.

[0127] Here, viscosity can be measured using a commercially available viscometer for measuring the viscosity of liquids, for example, by referring to the method described in JIS K 7117-2, under conditions where the composition is at a temperature of 25°C. Preferably, a cone-plate type rotational viscometer is used, and preferably the same type of viscometer with a standard cone rotor of 1°34' × R24 can be used to measure viscosity under conditions where the composition is at a temperature of 25°C. An example of such a rotational viscometer is the TVE-25L manufactured by Toki Sangyo Co., Ltd.

[0128] [Exfoliation layer] The release layer of the present invention can be manufactured by a method comprising the steps of forming a resin film on a substrate using the release layer forming composition (resin film forming step) and exposing a predetermined area of ​​the resin film with ultraviolet light (exposure step).

[0129] In the resin film formation process, one method for forming the resin film is to apply the release layer forming composition onto a substrate and then bake it. In this invention, the substrate refers to a material on which the release layer forming composition of the present invention is applied, and which is used in the manufacture of flexible electronic devices and the like.

[0130] Examples of substrates include glass, metal (such as silicon wafers), and slate, but glass is particularly preferred because the release layer obtained from the release layer forming composition of the present invention has sufficient adhesion to it. The substrate surface may be composed of a single material or of two or more materials. Examples of the substrate surface being composed of two or more materials include a configuration in which a certain area of ​​the substrate surface is composed of one material and the rest of the surface is composed of other materials, and a configuration in which a patterned material such as a dot pattern or a line and space pattern is present in the other materials across the entire substrate surface.

[0131] The coating method is not particularly limited, but examples include slit coating, cast coating, spin coating, blade coating, dip coating, roll coating, bar coating, die coating, inkjet, and printing methods (relief printing, intaglio printing, planographic printing, screen printing, etc.).

[0132] Examples of equipment used for firing include hot plates and ovens. The heating atmosphere may be under air or an inert gas, and may be under normal pressure or reduced pressure.

[0133] The firing temperature is typically 50 to 250°C. The firing time varies depending on the temperature and cannot be specified in general terms, but it is usually between 1 minute and 5 hours. The firing process may also include firing at temperatures below the above range, as long as the maximum temperature remains within that range.

[0134] A preferred example of the heating method in the present invention is to heat at 50-150°C for 1 minute to 1 hour, and then continue to increase the heating temperature to 100-250°C for 5 minutes to 4 hours. A particularly preferred example of the heating method is to heat at 50-150°C for 1 minute to 1 hour, and then heat at 150-250°C for 5 minutes to 2 hours. Furthermore, another example of a more preferred heating method is to heat at 50-150°C for 1 minute to 30 minutes, and then heat at 200-250°C for 5 minutes to 1 hour.

[0135] In the exposure step, ultraviolet light may be irradiated over the entire surface of the resin film, or it may be irradiated through a mask having a predetermined pattern. When irradiated through a mask, a release layer with a pattern such as a dot pattern or a line and space pattern is obtained.

[0136] The ultraviolet light is not particularly limited as long as it has a wavelength capable of causing a photofleece rearrangement, but preferably has a wavelength of 200 to 400 nm, specifically 254 nm. The irradiation dose is 10 to 2,000 mJ / cm². 2 Preferably, 50-1,000 mJ / cm² 2 This is preferable.

[0137] When forming the release layer of the present invention on a substrate, the release layer may be formed on a part of the substrate's surface or on the entire surface. Examples of forming the release layer on a part of the substrate's surface include forming the release layer only in a predetermined area of ​​the substrate's surface, and forming the release layer in a pattern such as a dot pattern or a line-and-space pattern on the entire substrate surface or a predetermined area.

[0138] The thickness of the release layer is typically about 0.01 to 50 μm, preferably about 0.01 to 20 μm, and more preferably about 0.01 to 5 μm, from the viewpoint of productivity, and the desired thickness is achieved by adjusting the thickness of the coating film before heating.

[0139] The release layer of the present invention has excellent adhesion to a substrate, particularly a glass substrate, as well as appropriate adhesion and release properties to a resin substrate. Therefore, the release layer of the present invention can be suitably used in the manufacturing process of flexible electronic devices to release the resin substrate from the substrate, together with circuits and the like formed on the resin substrate, without damaging the resin substrate of the device.

[0140] [Method for manufacturing resin substrates] An example of a method for manufacturing a flexible electronic device using the release layer of the present invention will be described. First, a release layer is formed in a predetermined region on a substrate using the release layer forming composition of the present invention by the method described above. A resin substrate forming solution for forming a resin substrate is applied to the entire surface of the substrate on which this release layer has been formed in the predetermined region, and the resulting coating film is fired to form a resin substrate fixed to the substrate via the release layer of the present invention.

[0141] The firing temperature of the coating film is set appropriately according to the type of resin, etc., but it is preferable that the maximum temperature during firing be 200 to 250°C, more preferably 210 to 250°C, and even more preferably 220 to 240°C. By setting the maximum temperature during firing in the production of the resin substrate within this range, the adhesion between the release layer (which is the base material) and the substrate, as well as the appropriate adhesion and release properties between the release layer and the resin substrate, can be further improved. In this case as well, as long as the maximum temperature falls within the aforementioned range, a firing step at a lower temperature may be included.

[0142] Examples of the aforementioned resin substrate include a resin substrate made of a thermosetting film containing an epoxy compound, a resin substrate made of an acrylic polymer, and a resin substrate made of a cycloolefin polymer. The resin substrate can be formed by any conventional method. Furthermore, it is preferable that the resin substrate has a light transmittance of 80% or more at a wavelength of 400 nm.

[0143] Next, a desired circuit is formed on the resin substrate fixed to the substrate via the release layer of the present invention, and then, for example, the resin substrate is cut along the release layer, and the resin substrate is peeled off from the release layer together with the circuit, thereby separating the resin substrate from the substrate. At this time, a part of the substrate may be cut together with the release layer. By using the release layer of the present invention, the resin substrate can be peeled off from the release layer with a peeling force of 1.0 N / 25 mm or less. [Examples]

[0144] The present invention will be described in more detail below with reference to synthesis examples, preparation examples, examples, and comparative examples, but the present invention is not limited to the following examples.

[0145] The compounds used in the following example are as follows: PGME: Propylene glycol monomethyl ether PGMEA: Propylene glycol monomethyl ether acetate PL-LI: 1,3,4,6-tetrakis(methoxyethyl) glycoluryl (manufactured by Ornex, trade name: POWDERLINK 1174) PPTS: Pyridinium p-toluenesulfonate MMA: Methyl methacrylate HPMA: 2-hydroxypropyl methacrylate HEMA: 2-hydroxyethyl methacrylate ADMA: 2-adamantyl methacrylate DCPMA: Dicyclopentanyl methacrylate PhMA: Phenyl methacrylate PhA: Phenyl Acrylate AcSt: 4-acetoxystyrene NMA: 2-naphthyl methacrylate HFiPMA: 1,1,1,3,3,3-Hexafluoroisopropyl Methacrylate AIBN: Azobisisobutyronitrile DT: Dodecanethiol

[0146] Furthermore, the weight-average molecular weight (Mw) of the polymer was measured using a GPC instrument manufactured by Shimadzu Corporation (columns: Shodex® KF803L and KF804L (manufactured by Showa Denko K.K.); eluent: THF; flow rate: 1.0 mL / min; column temperature: 40°C; Mw: standard polystyrene equivalent value).

[0147] [1] Synthesis of component (A) [Synthesis Example 1] A polymer solution was obtained by dissolving 5.00 g (21.18 mmol) of HFiPMA, 1.53 g (10.59 mmol) of HPMA, 3.43 g (21.18 mmol) of PhMA, 0.54 g (2.65 mmol) of AIBN as a polymerization catalyst, and 0.43 g (2.65 mmol) of DT as a chain transfer agent in 50.0 g of PGME and reacting under heating reflux for 20 hours. The obtained polymer solution was gradually added dropwise to a mixed solvent of 200 g of water and 200 g of methanol to precipitate a solid. The precipitated solid was filtered off and dried under reduced pressure to obtain polymer (PA-1). The Mw of the acrylic copolymer (PA-1) was 6,400.

[0148] [Synthesis Examples 2-7] Polymers (PA-2) to (PA-7) were obtained in the same manner as in Synthesis Example 1, except that the types and amounts of raw material compounds were as shown in Table 1 below. The Mw of the obtained polymers is shown in Table 1.

[0149] [Table 1]

[0150] [2] Synthesis of component (B) [Synthesis Example 8] 50 g of monoallyl diglycidyl isocyanuric acid (manufactured by Shikoku Chemicals, Inc.), 33.2 g of 5,5-diethylbarbituric acid, and 2.0 g of benzyltriethylammonium chloride were dissolved in 41 g of PGME3, and the mixture was reacted at 130°C for 24 hours to obtain a polyurea-containing solution. The obtained polyurea-containing solution was gradually added dropwise to 2,000 g of hexane to precipitate a solid. The precipitated solid was filtered off and dried under reduced pressure to obtain polyurea (L1). GPC analysis revealed that the Mw of polyurea (L1) was 8,000.

[0151] [Synthesis Example 9] An acrylic copolymer solution was obtained by dissolving 100.0 g of MMA, 11.1 g of HEMA, and 5.6 g of AIBN as a polymerization catalyst in 450.0 g of PGME and reacting them at 80°C for 20 hours. The obtained acrylic copolymer solution was gradually added dropwise to 5,000 g of hexane to precipitate a solid. The precipitated solid was filtered off and dried under reduced pressure to obtain acrylic polymer (L2). GPC analysis revealed that the Mw of acrylic polymer (L2) was 7,600.

[0152] [3] Preparation of composition for forming resin substrate [Preparation Example 1] Preparation of resin substrate forming composition F1 10 g of Zeonor® 1020R (cycloolefin polymer manufactured by Nippon Zeon Co., Ltd.) and 3 g of Epolid® GT401 (manufactured by Daicel Corporation) were added to a round-bottom flask containing 100 g of carbon tetrachloride. This solution was stirred under a nitrogen atmosphere for 24 hours to dissolve and prepare resin substrate formation composition F1.

[0153] [4] Preparation of composition for forming a release layer [Example 1-1] A polymer (PA-1) was mixed as component (A) at 7.5 parts by mass, polyurea (L1) as component (B) at 100 parts by mass, PL-LI as component (C) at 25 parts by mass, and PPTS as component (D) at 3 parts by mass. PGME and PGMEA were added as solvents in a mass ratio of PGME:PGMEA = 70:30 to prepare a release layer forming composition (A-1) with a solid content concentration of 5.0% by mass.

[0154] [Examples 1-2 to 1-7, Comparative Examples 1-1, 1-2] Except for the types and amounts of each component as shown in Table 2, the release layer forming compositions A-2 to A-9 were prepared in the same manner as in Example 1-1.

[0155] [Table 2]

[0156] [5] Preparation and evaluation of the delamination layer [Example 2-1] Using a spin coater (conditions: rotation speed 800 rpm for approximately 30 seconds), the release layer formation composition (A-1) was applied onto a glass substrate (Corning Eagle XG, 100 mm × 100 mm × 0.5 mm, the same applies hereafter). The resulting coating was heated on a hot plate at 100°C for 2 minutes, and then on a hot plate at 230°C for 10 minutes to form a release layer approximately 0.1 μm thick on the glass substrate. A portion of this release layer was exposed to ultraviolet light containing a 254 nm emission line at a rate of 100 mJ / cm using a high-pressure mercury lamp. 2 Irradiated with (254nm equivalent) light. Subsequently, using a spin coater (conditions: rotation speed 200 rpm for approximately 15 seconds), the resin substrate forming composition F1 was applied to the entire surface of the glass substrate where the release layer had formed in a predetermined area. The resulting coating was heated on a hot plate at 80°C for 2 minutes, and then heated on a hot plate at 230°C for 30 minutes to form a resin substrate with a thickness of approximately 3 μm on the release layer, thereby obtaining a resin substrate and a glass substrate with a release layer.

[0157] [Examples 2-2 to 2-7, Comparative Examples 2-1, 2-2] Except for using release layer forming compositions (A-2) to (A-9) instead of release layer forming composition (A-1), resin substrates and glass substrates with release layers of Examples 2-2 to 2-6, Comparative Examples 2-1 and 2-2 were obtained in the same manner as in Example 2-1.

[0158] [Evaluation of peeling force] The resin substrates and glass substrates with release layers obtained in Examples 2-1 to 2-7 and Comparative Examples 2-1 and 2-2 were cut into 25mm x 50mm strips using a cutter. Furthermore, cellophane tape (registered trademark) (CT-24, manufactured by Nichiban Co., Ltd.) was applied, and the strips were peeled off using an Autograph AGS-X500N (manufactured by Shimadzu Corporation) at a peeling angle of 90° and a peeling speed of 300mm / min, and the peeling force was measured. The evaluation result is referred to as "peeling force," and the results are summarized in Table 3.

[0159] [Table 3]

[0160] As shown in Table 3, the peeling layer of the example showed low peeling force in the unexposed area, while the exposed area showed higher peeling force than the unexposed area. On the other hand, the peeling layer of the comparative example showed low peeling force regardless of whether it was exposed or not.

Claims

1. A composition for forming a release layer comprising (A) a polymer containing repeating units having photosensitive groups that undergo photofleece rearrangement and (B) a resin having hydroxyl groups or carboxyl groups, The repeating unit having a photosensitive group that undergoes the photofleece rearrangement is derived from a monomer represented by the following formula (a1) or (a2): (B) The resin having a hydroxyl group or a carboxyl group is a polyurea having a hydroxyl group, an acrylic polymer having a hydroxyl group or a carboxyl group, a polyester having a hydroxyl group, or cellulose or a derivative thereof having a hydroxyalkyl group. Composition for forming a release layer. 【Chemistry 1】 (In the formula, Ar 1 is a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 2-biphenylyl group, a 3-biphenylyl group, or a 4-biphenylyl group, and some or all of the hydrogen atoms of these groups may be substituted with C1-C6 alkyl groups, C1-C6 alkoxy groups, chlorine atoms, or bromine atoms, but at least one of the ortho and para positions of the oxygen atom in the formula is a hydrogen atom; Ar 2 These are 1,2-phenylene group, 1,3-phenylene group, 1,4-phenylene group, 1,2-naphthylene group, 1,3-naphthylene group, 1,4-naphthylene group, 1,5-naphthylene group, 1,6-naphthylene group, 1,7-naphthylene group, 1,8-naphthylene group, 2,3-naphthylene group, 2,6-naphthylene group, 2,2'-biphenylylene group, 2,3'-biphenylylene group, The group is a 2,4'-biphenylylene group, a 3,3'-biphenylylene group, a 3,4'-biphenylylene group, or a 4,4'-biphenylylene group, where some or all of the hydrogen atoms of these groups may be substituted with a C1-C6 alkyl group, a C1-C6 alkoxy group, a chlorine atom, or a bromine atom, but at least one of the ortho and para positions of the oxygen atom in the formula is a hydrogen atom; R 1 is an alkyl group or phenyl group having 1 to 6 carbon atoms; X 1 and X 2 Each of these is independently a single bond or an alkylene group having 1 to 20 carbon atoms, and one or more of these alkylene groups are -CH 2 - may be substituted with at least one group selected from -O-, -C(=O)-O-, and -O-C(=O)-; A 1 and A 2 These are each independently radical polymerizable groups represented by the following formula (A-1). 【Chemistry 2】 (RA is independently either a hydrogen atom or a methyl group.)

2. (A) The resin composition for forming a release layer according to claim 1, wherein the polymer further comprises repeating units derived from a monomer represented by the following formula (b) and repeating units derived from a monomer represented by the following formula (c). 【Transformation 3】 (wherein, R A is each independently a hydrogen atom or a methyl group; R B is a branched alkyl group having 3 or 4 carbon atoms, in which at least one hydrogen atom is substituted with a fluorine atom; R C (This refers to a hydroxyalkyl group having 2 to 10 carbon atoms.)

3. Furthermore, the composition for forming a release layer according to claim 1, further comprising a crosslinking agent selected from compounds having a nitrogen atom substituted with a hydroxyalkyl group and / or an alkoxymethyl group.

4. Furthermore, the composition for forming a peeling layer according to claim 1, further comprising (D) a crosslinking catalyst.

5. A release layer obtained from the release layer forming composition according to any one of claims 1 to 4.

6. A method for forming a release layer, comprising the steps of forming a resin film on a substrate using a release layer forming composition according to any one of claims 1 to 4, and exposing a predetermined region of the resin film with ultraviolet light.

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