Release layer forming composition and release layer

Abstract

To provide a composition for peeling layer formation which enables formation of a device composed of a resin substrate on a peeling layer, and gives the peeling layer easily peeled at an interface between the peeling layer and the device composed of the resin substrate.SOLUTION: A composition for peeling layer formation contains (A) a polymer containing 1-70 mol% of a monomer having a Michael donor group with respect to 100 mol% of the total monomer units, (B) a crosslinking agent having a Michael acceptor group, and (C) a Michael addition reaction catalyst.SELECTED DRAWING: None

Description

[Technical field]

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

[0002] In recent years, electronic devices are required to be bendable in addition to being thin and lightweight, which necessitates the use of lightweight, flexible plastic substrates instead of conventional heavy, brittle, and inflexible glass substrates.

[0003] In particular, new generation displays require the development of active matrix type full color TFT display panels using lightweight flexible plastic substrates (hereinafter also referred to as resin substrates). In addition, for touch panel type displays, materials that correspond to flexibility, such as transparent electrodes and resin substrates of touch panels used in combination with display panels, have been developed. As for transparent electrodes, other transparent electrode materials have been proposed, such as transparent conductive polymers that can be bent, such as PEDOT, metal nanowires, and mixtures thereof, in place of the conventionally used ITO (Patent Documents 1 to 4).

[0004] Meanwhile, the base material of touch panel films has also changed from glass to sheets made of plastics such as polyethylene terephthalate (PET), polyimide, cycloolefin, and acrylic, and transparent flexible touch screen panels with flexibility have been developed (Patent Documents 5 to 7).

[0005] In general, in order to ensure stable production of flexible touch screen panels, a release (adhesive) layer is formed on a support substrate such as a glass substrate, a device composed of a resin substrate or the like is formed on the release (adhesive) layer, and then the device is peeled off from the adhesive layer (Patent Document 8).

[0006] As the release layer, for example, a curable resin compound containing a specific polymer and a crosslinking agent has been described (Patent Documents 9 to 10). While these release layers can be easily peeled off from the support substrate, the peeling occurs at the interface between the support substrate and the release layer, and therefore the release layer remains on the device side, which may adversely affect the device fabrication process and transparency. [Prior art documents] [Patent documents]

[0007] [Patent Document 1] International Publication No. 2012 / 147235 [Patent Document 2] JP 2009-283410 A [Patent Document 3] Special Publication No. 2010-507199 [Patent Document 4] JP 2009-205924 A [Patent Document 5] International Publication No. 2017 / 002664 [Patent Document 6] International Publication No. 2016 / 160338 [Patent Document 7] JP 2015-166145 A [Patent Document 8] JP 2016-531358 A [Patent Document 9] International Publication No. 2018 / 033995 [Patent Document 10] International Publication No. 2019 / 159248 Summary of the Invention [Problem to be solved by the invention]

[0008] The present invention has been made in consideration of the above circumstances, and aims to provide a composition for forming a release layer that can form a device composed of a resin substrate or the like on a release layer, and that provides a release layer that easily peels off at the interface between the release layer and the device composed of a resin substrate or the like. [Means for solving the problem]

[0009] As a result of extensive research to achieve the above-mentioned object, the present inventors have found that a release layer-forming composition containing (A) a polymer containing 1 to 70 mol % of a monomer having a Michael donor group, relative to 100 mol % of all monomer units, and (C) a Michael addition reaction catalyst, can form a device composed of a resin substrate, etc. on the release layer, and can reproducibly provide a release layer that is easily peeled off at the interface between the release layer and the device composed of a resin substrate, etc., and have completed the present invention.

[0010] That is, the present invention provides the following composition for forming a release layer and the following release layer. 1. (A) a polymer containing 1 to 70 mol % of a monomer having a Michael donor group relative to 100 mol % of all monomer units; (B) a crosslinker having a Michael acceptor group, and (C) Michael addition reaction catalyst, A release layer forming composition comprising: 2. A composition for forming a release layer according to claim 1, wherein the polymer (A) is a polymer obtained using at least one monomer selected from the group consisting of an acrylic acid ester compound, a methacrylic acid ester compound, a maleimide compound, an acrylamide compound, acrylonitrile, maleic anhydride, a styrene compound and a vinyl compound. 3. The release layer-forming composition according to 1 or 2, wherein the Michael donor group of the polymer (A) is an active methylene group or an active methine group. 4. The composition for forming a release layer according to any one of 1 to 3, wherein the monomer having no Michael donor group in the polymer (A) is a monomer having an alicyclic hydrocarbon group or a maleimide group. 5. The composition for forming a release layer according to any one of 1 to 4, wherein the Michael acceptor group of the crosslinking agent (B) is a (meth)acroyl group. 6. The resin composition for forming a release layer according to any one of 1 to 5, wherein the content of the crosslinking agent (B) is 1 to 100 parts by mass per 100 parts by mass of the polymer (A). 7. The resin composition for forming a release layer according to any one of 1 to 6, wherein the content of the catalyst (C) is 0.1 to 20 parts by mass per 100 parts by mass of the polymer (A). 8. A release layer obtained from any one of the compositions for forming a release layer recited in 1 to 7. 9. A laminate in which a resin substrate having a light transmittance of 80% or more at a wavelength of 400 nm is laminated on the release layer of 8. 10. The laminate of 9, wherein the resin substrate is a thermosetting film containing an epoxy compound. 11. A step of applying any one of the compositions for forming a release layer according to 1 to 7 to a substrate to form a release layer; forming a resin substrate having a light transmittance of 80% or more at a wavelength of 400 nm on the release layer; A step of peeling off the resin substrate with a peeling force of 0.4 N / 25 mm or less. A method for producing a resin substrate comprising the steps of: Effect of the Invention

[0011] By using the composition for forming a release layer of the present invention, a device composed of a resin substrate or the like can be formed on the release layer, and a release layer that easily peels off at the interface between the release layer and the device composed of the resin substrate or the like can be obtained with good reproducibility. In addition, in the manufacturing process of a flexible electronic device, it becomes possible to separate the resin substrate together with the circuit or the like formed on the substrate from the substrate without damaging the resin substrate formed on the substrate or the circuit or the like formed thereon. 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 having a resin substrate and improving its yield. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0012] The present invention will be described in further detail below. [Composition for forming release layer] The composition for forming a release layer of the present invention is characterized by comprising (A) a polymer containing 1 to 70 mol % of a monomer having a Michael donor group relative to 100 mol % of all monomer units, (B) a crosslinking agent having a Michael acceptor group, and (C) a Michael addition reaction catalyst.

[0013] [1] Component (A) The component (A) in the composition for forming a release layer of the present invention is a polymer containing 1 to 70 mol % of a monomer having a Michael donor group, relative to 100 mol % of all monomer units.

[0014] Examples of monomers constituting the polymer include acrylic acid ester compounds, methacrylic acid ester compounds, maleimide compounds, acrylamide compounds, acrylonitrile, maleic anhydride, styrene compounds, and vinyl compounds, but the present invention is not limited to these.

[0015] Examples of the Michael donor group include a mercapto group, an amino group, an active methylene group, and an active methine group. From the viewpoints of reactivity and storage stability, the active methylene group and the active methine group are preferred.

[0016] The term "active methylene group" refers to a methylene group (-CH2-) that has a carbonyl group adjacent thereto and is reactive to nucleophiles. In the present invention, the term "active methine group" refers to an active methylene group having a structure in which one hydrogen atom of the methylene group (-CH2-) is substituted with an alkyl group and is reactive to nucleophiles.

[0017] As the active methylene group and the active methine group, a group represented by the following formula (a1) is more preferable. [ka] (In the formula, R represents an alkyl group, an alkoxy group, or a phenyl group, and the dashed line represents a bond.)

[0018] The alkyl group may, for example, be an alkyl group having 1 to 20 carbon atoms, and an alkyl group having 1 to 5 carbon atoms is preferred. Specific examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, etc. Among these, a methyl group, an ethyl group, an n-propyl group, etc. are preferable.

[0019] Examples of the alkoxy group include alkoxy groups having 1 to 20 carbon atoms, and alkoxy groups having 1 to 5 carbon atoms are preferred. Specific examples of the alkoxy group include a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, an n-butoxy group, an i-butoxy group, an s-butoxy group, a t-butoxy group, etc. Among these, a methoxy group, an ethoxy group, an n-propoxy group, etc. are preferred.

[0020] Examples of the group represented by the formula (a1) include the following structures: In the structural formula, the dashed lines represent bonds. [ka]

[0021] The method of introducing the group represented by formula (a1) into each component includes a method of reacting a low molecular weight compound or polymer having a hydroxyl group with an acyl Meldrum's acid obtained by reacting Meldrum's acid with a carboxylic acid chloride. This method is publicly known. Here, R is preferably a methyl group in consideration of availability and peelability.

[0022] [ka] (In the formula, R is the same as defined above.)

[0023] Another method for introducing the group represented by formula (a1) into each component is to react a low molecular weight compound or polymer having a hydroxyl group with t-butyl acylacetate. This method is known. Here, R is preferably a methyl group in consideration of availability and peelability.

[0024] [ka] (In the formula, R is the same as defined above.)

[0025] Specific examples of monomers having a Michael donor group include 2-acetoacetoxyethyl acrylate and 2-acetoacetoxyethyl methacrylate.

[0026] The polymer that is the component (A) in the composition for forming a release layer of the present invention contains a monomer that does not have a Michael donor group.

[0027] Examples of the monomer having no Michael donor group include acrylic acid ester compounds, methacrylic acid ester compounds, maleimide compounds, acrylamide compounds, acrylonitrile, maleic anhydride, styrene compounds, vinyl compounds, etc. Specific examples of the monomer are listed below, but the present invention is not limited thereto.

[0028] Examples of monomers not having a Michael donor group include acrylic acid ester compounds such as methyl acrylate, ethyl acrylate, isopropyl acrylate, benzyl acrylate, naphthyl acrylate, anthryl acrylate, anthryl methyl acrylate, phenyl acrylate, glycidyl acrylate, 2,2,2-trifluoroethyl acrylate, t-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-tricyclodecyl acrylate, and 8-ethyl-8-tricyclodecyl acrylate; methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, benzyl methacrylate, naphthyl methacrylate, etc. methacrylic acid ester compounds such as methacrylate, anthryl methacrylate, anthryl methyl methacrylate, phenyl methacrylate, glycidyl methacrylate, 2,2,2-trifluoroethyl methacrylate, t-butyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, 2-methoxyethyl methacrylate, methoxytriethylene glycol methacrylate, 2-ethoxyethyl methacrylate, tetrahydrofurfuryl methacrylate, 3-methoxybutyl methacrylate, stearyl methacrylate, adamantyl methacrylate, 2-methyl-2-adamantyl methacrylate, γ-butyrolactone methacrylate, 2-propyl-2-adamantyl methacrylate, 8-methyl-8-tricyclodecyl methacrylate, and 8-ethyl-8-tricyclodecyl methacrylate; methyl vinyl ether, benzyl vinyl ether, vinyl naphthalene, vinyl carbazole, allyl glycidyl ether, 3-ethenyl-7-oxabicyclo[4.1.0] Vinyl compounds such as heptane, 1,2-epoxy-5-hexene, and 1,7-octadiene monoepoxide; styrene compounds such as styrene, methylstyrene, chlorostyrene, and bromostyrene; maleimide compounds such as maleimide, N-methylmaleimide, N-phenylmaleimide, and N-cyclohexylmaleimide.

[0029] From the viewpoints of heat resistance and hydrophobicity, it is desirable for the monomer not having a Michael donor group to be a monomer having an alicyclic hydrocarbon group or a maleimide group.

[0030] The monomer having an alicyclic hydrocarbon group is more preferably a (meth)acrylic acid ester having an alicyclic hydrocarbon group having a carbon number of 6 to 20. Examples of the alicyclic hydrocarbon group include a cyclohexyl group, a t-butylcyclohexyl group, an isobornyl group, a dicyclopentanyl group, a dicyclopentenyl group, and an adamantyl group.

[0031] Specific examples of monomers having an alicyclic hydrocarbon group include isobornyl methacrylate, isobornyl acrylate, dicyclopentanyl methacrylate, dicyclopentanyl acrylate, dicyclopentenyl methacrylate, dicyclopentenyl acrylate, adamantyl methacrylate, cyclohexyl methacrylate, and t-butylcyclohexyl methacrylate.

[0032] Specific examples of monomers having a maleimide group include maleimide, N-methylmaleimide, N-phenylmaleimide, and N-cyclohexylmaleimide.

[0033] In the polymer obtained by using the monomer having a Michael donor group (A), the content of the monomer having a Michael donor group is 1 to 70 mol%, preferably 2 to 60 mol%, and more preferably 3 to 50 mol%, based on 100 mol% of all monomer units. If the content of the monomer having a Michael donor group is too small, the solvent resistance and heat resistance of the release layer may decrease, and the release property may decrease. On the other hand, if the content is too large, the reaction with the resin substrate on the release layer may proceed, and the release property may decrease. The monomer constituting the polymer may be used alone or in combination of two or more.

[0034] The method for obtaining the polymer used in the composition for forming a release layer of the present invention is not particularly limited, but for example, it can be obtained by polymerization reaction at a temperature of 50 to 110°C in a solvent in which a monomer and a polymerization initiator coexist. The solvent used at that time is not particularly limited as long as it dissolves the monomer and the polymerization initiator. Specific examples include the solvents described below in the section on solvents.

[0035] The polymer thus obtained 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.

[0036] The polymer solution obtained as described above can be reprecipitated by adding it to hexane, diethyl ether, water, etc. under stirring, and the resulting precipitate can be filtered and washed, and then dried at room temperature or by heating under normal or reduced pressure to obtain a polymer powder. By such an operation, the polymerization initiator and unreacted monomers coexisting with the polymer can be removed, and as a result, a purified polymer powder can be obtained. If the polymer cannot be sufficiently purified by a single operation, the obtained powder can be redissolved in a solvent and the above operation can be repeated.

[0037] In the composition for forming a release layer of the present invention, the powder of the polymer may be used as the component (A) as it is, or the powder may be redissolved in, for example, a solvent described below and used in the form of a solution.

[0038] In the release layer-forming composition of the present invention, the polymer of component (A) may be a single type of polymer or a mixture of multiple types of polymers.

[0039] [2](B) Component The composition for forming a release layer of the present invention contains a crosslinking agent having a Michael acceptor group as the component (B).

[0040] Examples of Michael acceptor groups include (meth)acroyl groups and maleimide groups, i.e., CH2=CH-C(=O)-, CH(CH3)=CH-C(=O)- and maleimide groups.

[0041] As the crosslinking agent having a Michael acceptor group, the following low molecular weight compounds and high molecular weight compounds can be used. Examples of the low molecular weight compound include a polyfunctional acrylate compound and a bismaleimide compound.

[0042] Examples of polyfunctional acrylates include trifunctional (having three (meth)acryloyl groups) urethane (meth)acrylate compounds, tetrafunctional (having four (meth)acryloyl groups) urethane (meth)acrylate compounds, pentafunctional or higher (having five or more (meth)acryloyl groups) urethane (meth)acrylate compounds, trifunctional (having three (meth)acryloyl groups) (meth)acrylate compounds, tetrafunctional (having five (meth)acryloyl groups) (meth)acrylate compounds, and pentafunctional or higher (having five or more (meth)acryloyl groups) (meth)acrylate compounds.

[0043] As the trifunctional urethane (meth)acrylate compound, commercially available products can be used, and specific examples thereof include NK Oligo UA-7100 (manufactured by Shin-Nakamura Chemical Co., Ltd.); EBECRYL (registered trademark) 204, 205, 264, 265, 294 / 25HD, 1259, 4820, 8311, 8465, 8701, 9260, KRM (registered trademark) 8296, and 8667 (all manufactured by Daicel-Allnex Corporation); Shikoh (registered trademark) UV-7550B, 7000B, 7510B, 7461TE, and 2750B (all manufactured by Nippon Synthetic Chemical Industry Co., Ltd.).

[0044] As the tetrafunctional urethane (meth)acrylate compound, commercially available products can be used, and specific examples thereof include EBECRYL (registered trademark) 8210, 8405, KRM (registered trademark) 8528 (all manufactured by Daicel-Allnex Co., Ltd.); Shiko (registered trademark) UV-7650B (manufactured by Nippon Synthetic Chemical Industry Co., Ltd.); and the like.

[0045] Specific examples of the penta- or higher functional urethane (meth)acrylate include a urethane compound of pentaerythritol tri(meth)acrylate and hexamethylene diisocyanate, a urethane compound of pentaerythritol tri(meth)acrylate and toluene diisocyanate, a urethane compound of pentaerythritol tri(meth)acrylate and isophorone diisocyanate, and a urethane compound of dipentaerythritol penta(meth)acrylate and hexamethylene diisocyanate.

[0046] As the pentafunctional or higher urethane (meth)acrylate, commercially available products can be suitably used. Specific examples thereof include UA-306H, UA-306T, UA-306I, and UA-510H (all manufactured by Kyoeisha Chemical Co., Ltd.); NK Oligo U-6LPA, U-10HA, U-10PA, U-1100H, U-15HA, UA-53H, and UA-33H (all manufactured by Shin-Nakamura Chemical Co., Ltd.); EBECRYL (registered trademark) and KRM (registered trademark) 220, 1290, 5129, 8254, 8301R, KRM (registered trademark) 8200, 8200AE, 8904, and 8452 (all manufactured by Daicel-Allnex Co., Ltd.); Shikoh (registered trademark) UV-1700B, 6300B, 7600B, 7605B, 7610B, 7620EA, 7630B, 7640B, and 7650B (all manufactured by Nippon Synthetic Chemical Industry Co., Ltd.).

[0047] Examples of the trifunctional (meth)acrylate compound include 1,1,1-trimethylolethane tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, and glycerin tri(meth)acrylate.

[0048] As the trifunctional (meth)acrylate compound, commercially available products can be suitably used, and specific examples thereof include Viscoat #295 and #300 (all manufactured by Osaka Organic Chemical Industry Co., Ltd.); Light Acrylate TMP-A, PE-3A, and Light Ester TMP (all manufactured by Kyoeisha Chemical Co., Ltd.); NK Ester A-9300, A-9300-1CL, A-TMM-3, A-TMM-3L, A-TMM-3LM-N, A-TMPT, and TMPT (all manufactured by Shin-Nakamura Chemical Co., Ltd.); PETIA, PETRA, TMPTA, and EBECRYL (registered trademark) 180 (all manufactured by Daicel-Allnex Corporation).

[0049] Examples of the tetrafunctional (meth)acrylate compound include ditrimethylolpropane tetra(meth)acrylate and pentaerythritol tetra(meth)acrylate.

[0050] As the tetrafunctional (meth)acrylate compound, commercially available products can be suitably used, and specific examples thereof include Viscoat #300 (manufactured by Osaka Organic Chemical Industry Co., Ltd.); Light Acrylate PE-4A (manufactured by Kyoeisha Chemical Co., Ltd.); NK Ester AD-TMP, NK Ester A-TMMT (all manufactured by Shin-Nakamura Chemical Co., Ltd.); EBECRYL (registered trademark) 140, 1142, EBECRYL 180 (all manufactured by Daicel-Allnex Corporation).

[0051] Examples of the penta- or higher functional (meth)acrylate compound include dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and tripentaerythritol octa(meth)acrylate.

[0052] As the pentafunctional or higher (meth)acrylate compound, commercially available products can be suitably used, and specific examples thereof include Viscoat #802 (manufactured by Osaka Organic Chemical Industry Co., Ltd.); Light Acrylate DPE-6A (manufactured by Kyoeisha Chemical Co., Ltd.); NK Ester A-9550, NK Ester A-DPH (all manufactured by Shin-Nakamura Chemical Co., Ltd.); DPHA (manufactured by Daicel-Allnex Co., Ltd.); and the like.

[0053] The bismaleimide compound may, for example, be a compound represented by the following formula (3).

[0054] [ka]

[0055] In the formula, R 33 is an organic group selected from the group consisting of an aliphatic group, an aliphatic group containing a cyclic structure, and an aromatic group, or an organic group consisting of a combination of a plurality of organic groups selected from the group. 33may contain bonds such as ester bonds, ether bonds, amide bonds, and urethane bonds.

[0056] Examples of such bismaleimide compounds include N,N'-3,3-diphenylmethane bismaleimide, N,N'-(3,3-diethyl-5,5-dimethyl)-4,4-diphenyl-methane bismaleimide, N,N'-4,4-diphenylmethane bismaleimide, 3,3-diphenylsulfone bismaleimide, 4,4-diphenylsulfone bismaleimide, N,N'-p-benzophenone bismaleimide, N,N'-diphenylethane bismaleimide, N,N'-diphenylether bismaleimide, N,N'-(methylenedi-ditetrahydro (3-ethyl)-4,4-diphenylmethane bismaleimide, N,N'-(3,3-dimethyl)-4,4-diphenylmethane bismaleimide, N,N'-(3,3-diethyl)-4,4-diphenylmethane bismaleimide, N,N'-(3,3-dichloro)-4,4-diphenylmethane bismaleimide, N,N'-isophorone bismaleimide, N,N'-tolidine bismaleimide, N,N'-diphenylpropane bismaleimide, N,N'-naphthalene bismaleimide, N,N'-m-phenylene bismaleimide Imide, N,N'-5-methoxy-1,3-phenylenebismaleimide, 2,2-bis(4-(4-maleimidophenoxy)phenyl)propane, 2,2-bis(3-chloro-4-(4-maleimidophenoxy)phenyl)propane, 2,2-bis(3-bromo-4-(4-maleimidophenoxy)phenyl)propane, 2,2-bis(3-ethyl-4-(4-maleimidophenoxy)phenyl)propane, 2,2-bis(3-propyl-4-(4-maleimidophenoxy)phenyl)propane, 2,2-bis(3-isopropyl-4-(4-maleimidophenoxy)phenyl)propane, 2,2-bis(3-butyl-4-(4-maleimidophenoxy)phenyl)propane, 2,2-bis(3-methoxy-4-(4-maleimidophenoxy)phenyl)propane, 1,1-bis(4-(4-maleimidophenoxy)phenyl)ethane, 1,1-bis(3-methyl-4-(4-maleimidophenoxy)phenyl)ethane, 1,1-bis(3-chloro-4-(4-maleimidophenoxy)phenyl)ethane, 1,1-bis(3-bromo-4-(4-maleimidophenoxy)phenyl)ethane, 3,3-bis(4-(4-maleimidophenoxy)phenyl)pentane, 1,1,1,3,3,3-hexafluoro-2,2-bis(4-(4-maleimidophenoxy)phenyl)propane, 1,1,1,3,3,3-hexafluoro-2,2-bis(3,5-dimethyl-4-(4-maleimidophenoxy)phenyl)propane, 1,1,1,3,3,3-hexafluoro-2,2-bis(3,5-dibromo-4-(4-maleimidophenoxy)phenyl)propane midophenoxy)phenyl)propane, N,N'-ethylenedimaleimide, N,N'-hexamethylenebismaleimide, N,N'-dodecamethylenebismaleimide, N,N'-m-xylenebismaleimide, N,N'-p-xylenebismaleimide, N,N'-1,3-bismethylenecyclohexanebismaleimide, N,N'-2,4-tolylenebismaleimide, N,N'-2,6-tolylenebismaleimide, and the like.

[0057] Examples of the polymer compound include a polymer compound having a side chain in the molecule, the end of which is a polymerizable unsaturated bond. As such a polymer compound, a polymer compound having a (meth)acryloyl group in two or more side chains in the molecule is preferable.

[0058] Examples of the polymer compound include polymer compounds containing a (meth)acryloyl group, such as urethane acrylic, epoxy acrylic, and various (meth)acrylate-based polymer compounds, particularly polyfunctional polymer compounds containing three or more (meth)acryloyl groups. Among these polymer compounds, the polymer compounds containing a (meth)acryloyl group are preferred in the present invention.

[0059] As the polymer compound containing a (meth)acryloyl group, commercially available products can be suitably used, and specific examples thereof include ACRYL 8KX-077, 8KX-078, 8KX-089, 8KX-127, 8KX-128, 8KX-012C, 8KX-014C, 8KX-018C, 8KX-052C, 8KQ-2001, 8BR-600, 8UH-1006, and 8UH-1012 (all manufactured by Taisei Fine Chemical Co., Ltd.); SMP-220A, SMP-250A, SMP-360A, and SMP-550A (all manufactured by Kyoeisha Chemical Co., Ltd.).

[0060] The content of the (B) component is preferably 1 to 100 parts by mass, more preferably 2 to 50 parts by mass, based on 100 parts by mass of the polymer of the (A) component. When the content of the (B) component is within the above range, a release layer resin composition having high heat resistance and appropriate releasability can be obtained. When the content of the crosslinking agent is too small, the solvent resistance and heat resistance of the release layer can decrease, and the releasability can decrease. On the other hand, when the content is too large, a crosslinking reaction with the resin substrate on the release layer can proceed, and the releasability can decrease. The (B) crosslinking agent may be used alone or in combination of two or more types.

[0061] [3](C) component The release layer-forming composition of the present invention contains a Michael addition reaction catalyst as component (C).

[0062] More specifically, the Michael addition reaction catalyst includes the basic compounds shown below, but is not limited thereto. Examples of basic compounds include hydroxides of alkali metals such as sodium hydroxide and potassium hydroxide; alkoxides of alkali metals such as sodium methoxide and potassium ethoxide; quaternary ammonium hydroxides such as tetrabutylammonium hydroxide and benzyltrimethylammonium hydroxide; quaternary ammonium carbonates such as tetrabutylammonium carbonate, benzyltrimethylammonium carbonate, triethylmonomethylammonium 2-ethylhexanoate and tetrabutylammonium acetate; quaternary ammonium fluorides such as tetrabutylammonium fluoride and benzyltrimethylammonium fluoride; quaternary ammonium tetrahydroborate and benzyltrimethylammonium tetrahydroborate; tertiary amines such as tetramethylguanidine, 1,8-diazabicyclo[5.4.0]undecene-7 and diazabicyclo[4.3.0]nonene-5; and tertiary phosphines such as guanidine, azine and triphenylphosphine.

[0063] Furthermore, an acidic compound may be added together with the Michael addition reaction catalyst in order to improve storage stability during storage. In particular, when a strong base compound with high catalytic activity is used, the addition of an acidic compound is effective in improving storage stability. Examples of the acidic compound include low-boiling carboxylic acids such as acetic acid, formic acid, and propionic acid, and high-boiling carboxylic acids such as monochloroacetic acid and octanoic acid.

[0064] In the present invention, among these Michael addition reaction catalysts, quaternary ammonium carbonates, quaternary ammonium hydroxides, and tertiary amines are more preferred from the viewpoints of reactivity and storage stability.

[0065] The content of the (C) component is preferably 0.1 to 20 parts by mass, more preferably 0.1 to 15 parts by mass, based on 100 parts by mass of the polymer of the (A) component. If the content of the (C) component is within the above range, a release layer resin composition that provides a release layer having high heat resistance and appropriate releasability can be obtained. The (C) crosslinking catalyst may be used alone or in combination of two or more kinds.

[0066] [4] Other additives The release layer forming composition of the present invention may contain a surfactant as necessary. By adding a surfactant, the coating property of the release layer forming composition on the substrate can be improved. As the surfactant, a known surfactant such as a nonionic surfactant, a fluorine-based surfactant, or a silicone-based surfactant can be used.

[0067] Specific examples of the nonionic surfactant include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, and polyoxyethylene oleyl ether; polyoxyethylene alkylaryl ethers such as polyoxyethylene octyl phenyl ether and polyoxyethylene nonyl phenyl 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.

[0068] Examples of the fluorine-based surfactants include F-TOP (registered trademark) EF301, EF303, and EF352 (manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd.), Megafac (registered trademark) F171, F173, F554, F559, F563, R-30, R-40, R-40-LM, and DS-21 (manufactured by DIC Corporation), Fluorad FC430 and FC431 (manufactured by 3M), Asahiguard (registered trademark) AG710, Surflon (registered trademark) S-382, SC101, SC102, SC103, SC104, SC105, and SC106 (manufactured by AGC Corporation).

[0069] Furthermore, examples of silicone surfactants include organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.).

[0070] These surfactants may be used alone or in combination of two or more. When a surfactant is used, the amount of the surfactant used is preferably 0.0001 to 1 part by mass, and more preferably 0.001 to 0.5 parts by mass, based on 100 parts by mass of the (A) polymer.

[0071] In addition, the composition for forming a release layer according to an embodiment of the present invention may contain other additives such as silane coupling agents, rheology adjusters, pigments, dyes, storage stabilizers, defoamers, and antioxidants, as long as the effects of the present invention are not impaired.

[0072] [5] Solvent The release layer-forming composition of the present invention may contain a solvent. The solvent is not particularly limited in type, structure, etc., so long as it has the ability to dissolve components (A), (B), and (C), and other additives used as necessary. In the present invention, glycol ether-based solvents having 3 to 20 carbon atoms, ester-based solvents having 3 to 20 carbon atoms, ketone-based solvents having 3 to 20 carbon atoms, and amide-based solvents are preferred.

[0073] Specific examples of glycol ether solvents 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-based 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. The solvent may be used alone or in combination of two or more.

[0074] The content of the solvent 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, and even more preferably 0.5 to 10% by mass. The solid content is a general term for all components of the composition for forming a release layer other than the solvent.

[0075] The method for preparing the composition for forming a release layer of the present invention is not particularly limited, and examples thereof include a method in which a solution of component (A) dissolved in a solvent is mixed with components (B) and (C) and, if desired, other additives, etc. in a predetermined ratio to prepare a homogeneous solution, and a method in which, if necessary, other additives are further added and mixed at an appropriate stage of the preparation method. The prepared solution of the composition for forming the release layer is preferably filtered using a filter having a pore size of about 0.2 μm before use.

[0076] The viscosity of the release layer-forming composition of the present invention is appropriately set taking into consideration the thickness of the release layer to be produced, etc., but when the objective is to reproducibly obtain a film having a thickness of about 0.01 to 5 μm, 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.

[0077] Here, the viscosity can be measured using a commercially available viscometer for measuring the viscosity of liquids, for example, by referring to the procedure described in JIS K7117-2, at a composition temperature of 25° C. Preferably, a cone-plate type rotational viscometer is used as the viscometer, and preferably the same type of viscometer is used with a standard cone rotor of 1°34′×R24, and the viscosity can be measured at a composition temperature of 25° C. An example of such a rotational viscometer is TVE-25L manufactured by Toki Sangyo Co., Ltd.

[0078] [Peeling layer] The release layer can be obtained by a baking method including a step of applying the composition for forming the release layer of the present invention onto a substrate and then baking the composition at 100 to 280°C. In this case, the firing time cannot be generally defined because it varies depending on the temperature, but is usually 1 minute to 5 hours. Furthermore, the firing step may include a step of firing at a temperature lower than the maximum temperature, as long as the maximum temperature is within the above range.

[0079] A preferred example of the heating mode in the present invention is to heat at 50 to 150° C. for 1 minute to 1 hour, and then increase the heating temperature to 100 to 280° C. for 5 minutes to 4 hours. A particularly preferred example of the heating mode is to heat at 50 to 150° C. for 1 minute to 1 hour, and then heat at 150 to 280° C. for 5 minutes to 2 hours. Another preferred example of the heating mode is to heat at 50 to 150° C. for 1 minute to 30 minutes, and then heat at 200 to 280° C. for 5 minutes to 1 hour.

[0080] When the release layer of the present invention is formed on a substrate, the release layer may be formed on a part of the substrate surface or on the entire substrate surface. The form of forming the release layer on a part of the substrate surface includes a form in which the release layer is formed only on a predetermined area of ​​the substrate surface, and a form in which the release layer is formed on the entire substrate surface in a pattern such as a dot pattern or a line and space pattern. In the present invention, the substrate refers to a substrate on whose surface 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.

[0081] Examples of the substrate (base material) include glass, metal (such as silicon wafer), slate, etc., but glass is particularly preferred because the release layer obtained from the composition for forming a release layer according to the present invention has sufficient adhesion to it. The substrate surface may be composed of a single material, or may be composed of two or more materials. The substrate surface may be composed of two or more materials in the form in which a certain range of the substrate surface is composed of a certain material and the remaining surface is composed of another material, or in which a material in a pattern such as a dot pattern or a line and space pattern is present in another material on the entire substrate surface.

[0082] The coating method is not particularly limited, but examples thereof include cast coating, spin coating, blade coating, dip coating, roll coating, bar coating, die coating, inkjet printing, and printing methods (relief printing, intaglio printing, planographic printing, screen printing, etc.).

[0083] Examples of the heating device include a hot plate, an oven, etc. The heating atmosphere may be air or an inert gas, and may be normal pressure or reduced pressure.

[0084] The thickness of the release layer is usually about 0.01 to 50 μm, and from the viewpoint of productivity, it is preferably about 0.01 to 20 μm, more preferably about 0.01 to 5 μm. The desired thickness is achieved by adjusting the thickness of the coating film before heating.

[0085] The release layer of the present invention has good releasability from a resin substrate provided thereon, and therefore can be suitably used in a manufacturing process for a flexible electronic device to peel off the resin substrate together with circuits and the like formed on the resin substrate from a base without damaging the resin substrate.

[0086] 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 on a glass substrate by the above-mentioned method using the composition for forming a release layer of the present invention. A resin substrate forming solution for forming a resin substrate is applied onto the release layer, and the resulting coating is baked to form a resin substrate fixed to the glass substrate via the release layer of the present invention.

[0087] The baking temperature of the coating film is appropriately set depending on the type of resin, etc., but in the present invention, the maximum temperature during baking is preferably 200 to 250° C., more preferably 210 to 250° C., and even more preferably 220 to 240° C. By setting the maximum temperature during baking in the preparation of the resin substrate within this range, the peelability between the release layer and the resin substrate can be further improved. In this case, too, a step of baking at a temperature lower than the maximum temperature may be included as long as the maximum temperature is within the above range.

[0088] It is preferable to form the resin substrate so as to completely cover the release layer and with an area larger than that of the release layer. Examples of the 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 may be formed according to a conventional method. In addition, it is preferable that the resin substrate has a light transmittance of 80% or more at a wavelength of 400 nm.

[0089] Next, a desired circuit is formed as necessary on the resin substrate fixed to the base 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 together with the circuit is peeled off from the release layer to separate the resin substrate from the base. At this time, a part of the base 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 0.4 N / 25 mm or less. EXAMPLES

[0090] 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.

[0091] The abbreviations used in the following examples have the following meanings.

[0092] [Polymer raw materials] ADMA: 2-adamantyl methacrylate DCPMA: dicyclopentanyl methacrylate EGAMA: 2-(acetoacetyloxy)ethyl methacrylate PhMI: N-phenylmaleimide AIBN: Azobisisobutyronitrile

[0093] 〔solvent〕 CHN: Cyclohexanone

[0094] [(B) component] DPHA: Dipentaerythritol hexaacrylate (A-DPH, manufactured by Shin-Nakamura Chemical Co., Ltd.) A-TMPT: Trimethylolpropane triacrylate (A-TMPT, manufactured by Shin-Nakamura Chemical Co., Ltd.) AD-TMP: Ditrimethylolpropane tetraacrylate (AD-TMP, manufactured by Shin-Nakamura Chemical Co., Ltd.)

[0095] [(C) component] U-CAT: Triethylmonomethylammonium 2-ethylhexanoate (U-CAT18X, San-Apro Co., Ltd.)

[0096] [Measurement of molecular weight of polymer] The molecular weight of the acrylic copolymer in the polymerization examples was measured as follows using a room temperature gel permeation chromatography (GPC) apparatus (GPC-101) manufactured by Shodex Co., Ltd. and columns (KD-803, KD-805) manufactured by Shodex Co., Ltd. The number average molecular weight (hereinafter referred to as Mn) and weight average molecular weight (hereinafter referred to as Mw) are expressed in terms of polystyrene. Column temperature: 40℃ Eluent: Tetrahydrofuran Flow rate: 1.0mL / min Standard sample for creating calibration curve: Standard polystyrene manufactured by Showa Denko Co., Ltd. (molecular weight: approximately 197,000, 55,100, 12,800, 3,950, 1,260, 580)

[0097] (1) Synthesis of component (A) [Synthesis Example 1] ADMA 5.00g (22.70mmol) as a non-crosslinkable monomer, EGAMA 0.26g (1.19mmol) as a crosslinkable monomer, and AIBN 0.12g (0.72mmol) as a polymerization catalyst were dissolved in THF 50.0g, and reacted under heating and reflux for 20 hours to obtain an acrylic copolymer solution. The acrylic copolymer solution was gradually dropped into hexane 500.0g to precipitate a solid, which was then filtered and dried under reduced pressure to obtain an acrylic polymer (PA-1). The Mw of the obtained acrylic copolymer was 17,000.

[0098] [Synthesis Examples 2-8] Polymers (PA-2) to (PA-8) 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.

[0099] [Table 1]

[0100] (2) Preparation of composition for forming resin substrate [Preparation Example 1] 10 g of Zeonor (registered trademark) 1020R (a cycloolefin polymer manufactured by Zeon Corporation) and 3 g of Epolead (registered trademark) GT401 (manufactured by Daicel Corporation) were added to an eggplant flask containing 100 g of carbon tetrachloride as a solvent. The solution was stirred for 24 hours under a nitrogen atmosphere to dissolve the solution, thereby preparing a composition F1 for forming a resin substrate.

[0101] (2) Preparation of the composition for forming the release layer [Example 1-1] 100 parts by mass of the polymer PA-1 obtained in Synthesis Example 1 above was mixed as component (A), 5 parts by mass of DPHA as component (B), and 1 part by mass of U-CAT as component (C), and CHN was added thereto to prepare a composition (A-1) for forming a release layer having a solids concentration of 5.0% by mass.

[0102] [Examples 1-2 to 1-10, Comparative Examples 1-1 to 1-2] The same procedure as in Example 1-1 was carried out except that the types and amounts of each component were as shown in Table 2, to prepare release layer-forming compositions (A-2) to (A-12).

[0103] [Table 2]

[0104] (3) Preparation of release layer and resin substrate [Example 2-1] Using a spin coater (conditions: rotation speed 2,000 rpm for about 30 seconds), the composition for forming a release layer (A-1) was applied onto a glass substrate (Corning Eagle XG, 100 mm x 100 mm x 0.7 mm, the same applies below) as a base. The resulting coating film was heated at 100°C for 2 minutes using a hot plate, and then heated at 230°C for 30 minutes using a hot plate to form a release layer with a thickness of about 0.1 μm on the glass substrate, thereby obtaining a glass substrate with a release layer. Then, using a spin coater (conditions: rotation speed 200 rpm for about 15 seconds), the resin substrate forming composition F1 was applied onto the release layer (resin thin film) on the glass substrate. The resulting 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 with a thickness of about 3 μm on the release layer, thereby obtaining a glass substrate with a resin substrate and a release layer.

[0105] [Examples 2-2 to 2-10, Comparative Examples 2-1 to 2-2] The same procedure as in Example 2-1 was carried out except that (A-2) to (A-12) were used as the release layer-forming compositions, to obtain resin substrates / glass substrates with a release layer of Examples 2-2 to 2-10 and Comparative Examples 2-1 to 2-2.

[0106] [Evaluation of peel strength] The resin substrate and glass substrate with the release layer obtained above were cut into strips of 25 mm x 50 mm using a cutter. Cellotape (registered trademark) (CT-24, manufactured by Nichiban Co., Ltd.) was then applied, and the tape was peeled off at a peel angle of 90° and a peel speed of 300 mm / min using an autograph AGS-X500N (manufactured by Shimadzu Corporation) to measure the peel strength. If the tape could not be peeled off, it was deemed impossible to peel. The evaluation results were recorded as "peeling strength", and the results are summarized in Table 3.

[0107] [Evaluation of peeled interface] The thickness of the peeling layer remaining on the glass substrate after evaluation of the peeling force was measured using a stylus film thickness meter. The thickness was compared with the thickness when the peeling layer was formed to determine the peeling interface. The evaluation result was recorded as the "peeling interface", and when the remaining film ratio (remaining film ratio (%) = peeling layer film thickness after peeling / peeling layer film thickness when peeling layer was formed x 100) was 90% or more, it was recorded as the peeling layer / resin interface, when it was 10% or more but less than 90%, it was recorded as cohesive failure of the peeling layer, and when it was less than 10%, it was recorded as the glass substrate / peeling layer interface. The evaluation results are summarized in Table 3.

[0108] [Table 3]

[0109] From the results shown in Table 3, it was confirmed that the release layer of the Example exhibited low peeling force and was excellent in peelability. It was also confirmed that the release layer of the Example peeled off at the interface between the release layer and the resin substrate. On the other hand, it was found that the films of Comparative Examples 2-1 and 2-2 did not function as a release layer.

Claims

1. (A) a polymer containing 1 to 70 mol % of a monomer having a Michael donor group relative to 100 mol % of all monomer units; (B) a crosslinker having a Michael acceptor group, and (C) a Michael addition reaction catalyst; A release layer forming composition comprising:

2. The composition for forming a release layer according to claim 1, wherein the polymer (A) is a polymer obtained using at least one monomer selected from the group consisting of acrylic acid ester compounds, methacrylic acid ester compounds, maleimide compounds, acrylamide compounds, acrylonitrile, maleic anhydride, styrene compounds and vinyl compounds.

3. 3. The composition for forming a release layer according to claim 1, wherein the Michael donor group of the polymer (A) is an active methylene group or an active methine group.

4. The composition for forming a release layer according to any one of claims 1 to 3, wherein the monomer having no Michael donor group in the polymer (A) is a monomer having an alicyclic hydrocarbon group or a maleimide group.

5. 5. The composition for forming a release layer according to claim 1, wherein the Michael acceptor group of the crosslinking agent (B) is a (meth)acroyl group.

6. 6. The composition for forming a release layer according to claim 1, wherein the content of the crosslinking agent (B) is 1 to 100 parts by mass based on 100 parts by mass of the polymer (A).

7. 7. The composition for forming a release layer according to claim 1, wherein the content of the catalyst (C) is 0.1 to 20 parts by mass based on 100 parts by mass of the polymer (A).

8. A release layer obtained from the composition for forming a release layer according to any one of claims 1 to 7.

9. 9. A laminate comprising the release layer according to claim 8 and a resin substrate having a light transmittance of 80% or more at a wavelength of 400 nm laminated thereon.

10. 10. The laminate according to claim 9, wherein the resin substrate is a thermosetting film containing an epoxy compound.

11. A step of applying the composition for forming a release layer according to any one of claims 1 to 7 to a substrate to form a release layer; forming a resin substrate having a light transmittance of 80% or more at a wavelength of 400 nm on the release layer; and A step of peeling off the resin substrate with a peeling force of 0.4 N / 25 mm or less. A method for producing a resin substrate comprising the steps of:

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