JP2022133827A - Composition for peeling layer formation and peeling layer - Google Patents

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

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

In recent years, electronic devices are required to have a function of being able to be bent in addition to characteristics such as thinness and weight reduction. For this reason, it is required to use a lightweight flexible plastic substrate instead of the conventional heavy, fragile and unbendable glass substrate.

In particular, for new-generation displays, there is a demand for the development of active-matrix full-color TFT display panels using lightweight flexible plastic substrates (hereinafter also referred to as resin substrates). In addition, for touch panel displays, flexible materials such as transparent electrodes and resin substrates of touch panels used in combination with display panels have been developed. As the transparent electrode, 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 addition to the conventionally used ITO (Patent Document 1- 4).

On the other hand, the base material of the touch panel film has also changed from glass to polyethylene terephthalate (PET), polyimide, cycloolefin, acrylic and other plastic sheets, etc., and transparent flexible touch screen panels with flexibility have been developed ( Patent documents 5-7).

In general, for flexible touch screen panels, in order to ensure stable production, a peeling (adhesive) layer is prepared on a support substrate such as a glass substrate, and a device composed of a resin substrate or the like is prepared on top of that. , is produced by peeling the device from the adhesive layer (Patent Document 8).

As the release layer, for example, a curable resin compound containing a predetermined polymer and a cross-linking agent is described (Patent Documents 9 to 10). While these release layers can be easily peeled off from the support substrate, they are peeled off at the interface between the support substrate and the release layer, leaving the release layer on the device side, which may adversely affect the device fabrication process and transmittance. .

WO2012/147235 JP 2009-283410 A Japanese Patent Publication No. 2010-507199 JP 2009-205924 A WO2017/002664 WO2016/160338 JP 2015-166145 A JP 2016-531358 A WO2018/033995 WO2019/159248

The present invention has been made in view of the above-mentioned circumstances, and can form a device composed of a resin substrate or the like on a release layer, and can be easily peeled off at the interface between the release layer and the device composed of the resin substrate or the like. An object of the present invention is to provide a composition for forming a release layer that provides a release layer.

As a result of extensive studies to achieve the above object, the present inventors have found that (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 composition for forming a release layer containing a Michael addition reaction catalyst can form a device composed of a resin substrate or the like on the release layer, and can easily be formed at the interface between the release layer and the device composed of the resin substrate or the like. The inventors have found that a peeling layer that can be peeled off easily can be provided with good reproducibility, and have completed the present invention.

That is, the present invention provides the following release layer-forming composition and 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 cross-linking agent having a Michael acceptor group, and (C) a Michael addition reaction catalyst,
A composition for forming a release layer containing
2. (A) The polymer is 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. 1. The composition for forming a release layer, which is a polymer containing
3. (A) The release layer-forming composition of 1 or 2, wherein the Michael donor group of the polymer is an active methylene group or an active methine group.
4. (A) 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 is a monomer having an alicyclic hydrocarbon group or a maleimide group.
5. (B) The composition for forming a release layer according to any one of 1 to 4, wherein the Michael acceptor group of the cross-linking agent is a (meth)acryloyl group.
6. (B) The resin composition for forming a release layer according to any one of 1 to 5, wherein the content of the crosslinking agent is 1 to 100 parts by mass with respect to 100 parts by mass of the polymer (A).
7. (C) The resin composition for forming a release layer according to any one of 1 to 6, wherein the content of the catalyst 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 release layer-forming composition according to any one of 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 No. 8.
10. 9. The laminate of 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 1 to 7 to a substrate to form a release layer;
Manufacture of a resin substrate, comprising the steps of: forming a resin substrate having a light transmittance of 80% or more at a wavelength of 400 nm on the peeling layer; and peeling the resin substrate with a peeling force of 0.4 N/25 mm or less. Method.

By using the release layer-forming composition of the present invention, a device composed of a resin substrate or the like can be formed on the release layer, and the release can be easily performed at the interface between the release layer and the device composed of the resin substrate or the like. Layers can be obtained reproducibly. Further, in the manufacturing process of the flexible electronic device, it is possible to separate the resin substrate from the base together with the circuit etc. without damaging the resin substrate formed on the base and the circuit etc. provided thereon. It becomes possible. Therefore, the composition for forming a release layer of the present invention can contribute to speeding up the manufacturing process of flexible electronic devices having a resin substrate, improving the yield thereof, and the like.

The present invention will be described in more detail below.
[Composition for forming release layer]
The release layer-forming composition of the present invention comprises (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 (B) a Michael acceptor group. It is characterized by comprising a cross-linking agent and (C) a Michael addition reaction catalyst.

[1] Component (A) Component (A) in the release layer-forming composition 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. be.

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 limited to these. not to be

Michael donor groups include, for example, mercapto groups, amino groups, active methylene groups and active methine groups. Active methylene groups and active methine groups are preferred from the viewpoint of reactivity and storage stability.

The active methylene group means a methylene group ₍ --CH.sub.2--) having a carbonyl group at an adjacent position and having reactivity with a nucleophilic reagent. In the present invention, the active methine group has a structure in which one hydrogen atom of the methylene group ₍ --CH.sub.2--) in the active methylene group is substituted with an alkyl group, and exhibits reactivity with nucleophilic reagents. Say what you have.

（式中、Ｒは、アルキル基、アルコキシ基又はフェニル基を表し、破線は結合手を表す。） As the active methylene group and the active methine group, groups represented by the following formula (a1) are more preferable.

(In the formula, R represents an alkyl group, an alkoxy group or a phenyl group, and the dashed line represents a bond.)

The alkyl group includes, for example, an alkyl group having 1 to 20 carbon atoms, preferably an alkyl group having 1 to 5 carbon atoms.
Specific examples of alkyl groups include methyl, ethyl, n-propyl and i-propyl groups. Among them, a methyl group, an ethyl group, an n-propyl group and the like are preferable.

The alkoxy group includes, for example, an alkoxy group having 1 to 20 carbon atoms, and an alkoxy group having 1 to 5 carbon atoms is preferable.
Specific examples of alkoxy groups include methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, i-butoxy, s-butoxy and t-butoxy groups. Among them, methoxy group, ethoxy group, n-propoxy group and the like are preferable.

Examples of the group represented by the formula (a1) include the following structures. In the structural formulas, dashed lines represent bonds.

As a method for introducing the group represented by the formula (a1) into each component, a low-molecular-weight compound or polymer having a hydroxy group is reacted with acyl Meldrum's acid obtained by reacting Meldrum's acid with carboxylic acid chloride. method. This method is known. Here, R is preferably a methyl group in consideration of availability, peelability, and the like.

（式中、Ｒは、前記と同じである。）

(Wherein, R is the same as described above.)

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

（式中、Ｒは、前記と同じである。）

(Wherein, R is the same as described above.)

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

The polymer, which is the component (A) in the release layer-forming composition of the present invention, contains a monomer having no Michael donor group.

Examples of monomers having no Michael donor group include acrylic acid ester compounds, methacrylic acid ester compounds, maleimide compounds, acrylamide compounds, acrylonitrile, maleic anhydride, styrene compounds and vinyl compounds. Specific examples of the monomers are listed below, but the present invention is not limited to these.

Examples of monomers having no Michael donor group include methyl acrylate, ethyl acrylate, isopropyl acrylate, benzyl acrylate, naphthyl acrylate, anthryl acrylate, anthryl methyl acrylate, phenyl acrylate, glycidyl acrylate, 2,2,2-trifluoro ethyl 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 - acrylic acid ester compounds such as 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, 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 - Methacrylic acid ester compounds such as 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 -Vinyl compounds such as ethenyl-7-oxabicyclo[4.1.0]heptane, 1,2-epoxy-5-hexene, and 1,7-octadiene monoepoxide; styrene, methylstyrene, chlorostyrene, and bromo Styrene compounds such as styrene; maleimide, N-methylmaleimide, N-phenyl Examples include maleimide compounds such as nylmaleimide and N-cyclohexylmaleimide.

From the viewpoint of heat resistance and hydrophobicity, monomers having no Michael donor group are desirably monomers having an alicyclic hydrocarbon group or a maleimide group.

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

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, t-butyl cyclohexyl methacrylate and the like can be mentioned.

Specific examples of monomers having a maleimide group include maleimide, N-methylmaleimide, N-phenylmaleimide, N-cyclohexylmaleimide and the like.

(A) In the polymer obtained using the monomer having a Michael donor group, the content of the monomer having a Michael donor group is 1 to 70 mol% and 2 to 60 mol% with respect to 100 mol% of the total monomer units. mol % is preferred, and 3 to 50 mol % is more preferred. 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 be lowered, resulting in a decrease in releasability. On the other hand, if the content is excessively high, the reaction with the resin substrate or the like on the release layer may proceed, resulting in a decrease in releasability. The monomers constituting the polymer may be used singly or in combination of two or more.

The method for obtaining the polymer used in the release layer-forming composition of the present invention is not particularly limited. can get. At that time, the solvent used is not particularly limited as long as it dissolves the monomer, the polymerization initiator, and the like. Specific examples thereof include the solvents described in the solvent to be described later.

The polymer thus obtained is usually in the form of a solution dissolved in a solvent, and can be used as it is as a solution of component (A) in the present invention.

Alternatively, the solution of the polymer obtained as described above is added to hexane, diethyl ether, water, or the like under stirring to reprecipitate, and after filtering and washing the generated precipitate, Then, by drying at room temperature or by heating, a polymer powder can be obtained. By such an operation, the polymerization initiator and unreacted monomers coexisting with the polymer can be removed, and as a result, purified powder of the polymer can be obtained. If the purification cannot be sufficiently performed by one operation, the obtained powder may be redissolved in a solvent and the above operation may be repeated.

In the release layer-forming composition 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 a solvent described later, for example, and used in the form of a solution. may

In the release layer-forming composition of the present invention, as the polymer of component (A), a single type of polymer or a mixture of a plurality of types of polymers may be used.

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

Michael acceptor groups include, for example, (meth)acryloyl groups and maleimido groups, namely, CH ₂ =CH-C(=O)-, CH(CH ₃ )=CH-C(=O)- and maleimido groups. mentioned.

As the cross-linking agent having a Michael acceptor group, the following low-molecular-weight compounds and high-molecular-weight compounds can be used.
Examples of low-molecular-weight compounds include polyfunctional acrylate compounds and bismaleimide compounds.

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 more ( (Meth) urethane (meth) acrylate compounds (having 5 or more (meth) acryloyl groups), trifunctional (having 3 (meth) acryloyl groups) (meth) acrylate compounds, tetrafunctional (having 5 (meth) acryloyl groups) ) (meth)acrylate compounds and pentafunctional or higher (having 5 or more (meth)acryloyl groups) (meth)acrylate compounds.

Commercially available products can be used as trifunctional urethane (meth)acrylate compounds, and specific examples thereof include NK Oligo UA-7100 (manufactured by Shin-Nakamura Chemical Co., Ltd.); EBECRYL (registered trademark) 204 and 205. , 264, 265, 294/25HD, 1259, 4820, 8311, 8465, 8701, 9260, KRM (registered trademark) 8296, 8667 (all of these are Daicel Allnex Ltd.) (manufactured by Nippon Synthetic Chemical Industry Co., Ltd.);

As the tetrafunctional urethane (meth)acrylate compound, a commercially available product can be used, and specific examples thereof include EBECRYL (registered trademark) 8210, 8405, and KRM (registered trademark) 8528 (both of which are Daicel Ornex ( Co., Ltd.); Shiko (registered trademark) UV-7650B (manufactured by Nippon Synthetic Chemical Industry Co., Ltd.);

Specific examples of pentafunctional or higher urethane (meth)acrylates include urethanized products of pentaerythritol tri(meth)acrylate and hexamethylene diisocyanate, urethanized products of pentaerythritol tri(meth)acrylate and toluene diisocyanate, pentaerythritol tri Urethane compounds of (meth)acrylate and isophorone diisocyanate, urethan compounds of dipentaerythritol penta(meth)acrylate and hexamethylene diisocyanate, and the like can be mentioned.

Commercially available products can be suitably used as the pentafunctional or higher urethane (meth)acrylate, and specific examples include UA-306H, UA-306T, UA-306I, and UA-510H (all of which are Kyoeisha Chemical ( Co., Ltd.); NK Oligo U-6LPA, NK Oligo U-10HA, NK Oligo U-10PA, NK Oligo U-1100H, NK Oligo U-15HA, UA-53H, UA-33H (All of the above are Shin-Nakamura Chemical Industries ( Co., Ltd.); (manufactured by Nippon Synthetic Chemical Industry Co., Ltd.); are mentioned.

Trifunctional (meth)acrylate compounds include 1,1,1-trimethylolethane tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tri(meth)acrylate, and pentaerythritol tri(meth)acrylate. , glycerin tri(meth)acrylate and the like.

Commercially available products can be suitably used as the trifunctional (meth)acrylate compound. Specific examples thereof include Viscoat #295 and Viscoat #300 (both of which are manufactured by Osaka Organic Chemical Industry Co., Ltd.); Light Acrylate TMP -A, PE-3A, 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, TMPT (all manufactured by Shin-Nakamura Chemical Co., Ltd.); PETIA, PETRA, TMPTA, EBECRYL (registered trademark) 180 (all Daicel · Allnex Co., Ltd.) and the like.

Examples of tetrafunctional (meth)acrylate compounds include ditrimethylolpropane tetra(meth)acrylate and pentaerythritol tetra(meth)acrylate.

Commercially available products can be suitably used as the tetrafunctional (meth)acrylate compound. Specific examples thereof include Viscoat #300 (manufactured by Osaka Organic Chemical Industry Co., Ltd.); Light Acrylate PE-4A (Kyoeisha Chemical Co., Ltd.) NK Ester AD-TMP, A-TMMT (both of which are manufactured by Shin-Nakamura Chemical Co., Ltd.); EBECRYL (registered trademark) 140, 1142, and 180 (both of which are Daicel ) made) and the like.

Penta- or higher-functional (meth)acrylate compounds include dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and tripentaerythritol octa(meth)acrylate.

Commercially available products can be suitably used as the pentafunctional or higher (meth)acrylate compound. Specific examples thereof include Viscoat #802 (manufactured by Osaka Organic Chemical Industry Co., Ltd.); Light Acrylate DPE-6A (Kyoeisha Chemical ( NK Ester A-9550, NK Ester A-DPH (both of which are manufactured by Shin-Nakamura Chemical Co., Ltd.); DPHA (manufactured by Daicel Allnex Co., Ltd.);

Examples of the bismaleimide compound include compounds represented by the following formula (3).

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 these groups. . R ³³ may contain a bond such as an ester bond, an ether bond, an amide bond, or a urethane bond.

Examples of such bismaleimide compounds include N,N'-3,3-diphenylmethane bismaleimide and N,N'-(3,3-diethyl-5,5-dimethyl)-4,4-diphenyl-methane. bismaleimide, N,N'-4,4-diphenylmethanebismaleimide, 3,3-diphenylsulfonebismaleimide, 4,4-diphenylsulfonebismaleimide, N,N'-p-benzophenonebismaleimide, N,N'- diphenylethanebismaleimide, N,N'-diphenyletherbismaleimide, N,N'-(methylenedi-ditetrahydrophenyl)bismaleimide, N,N'-(3-ethyl)-4,4-diphenylmethanebismaleimide, N, N'-(3,3-dimethyl)-4,4-diphenylmethanebismaleimide, N,N'-(3,3-diethyl)-4,4-diphenylmethanebismaleimide, N,N'-(3,3- dichloro)-4,4-diphenylmethanebismaleimide, N,N'-isophoronebismaleimide, N,N'-tolysinebismaleimide, N,N'-diphenylpropanebismaleimide, N,N'-naphthalenebismaleimide, N, N'-m-phenylenebismaleimide, 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 noxy)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, 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.

Examples of the polymer compound include polymer compounds having a side chain in which one or more ends are polymerizable unsaturated bonds in the molecule. As such a polymer compound, a polymer compound having (meth)acryloyl groups in two or more side chains in the molecule is preferable.

Examples of the polymer compound include polymer compounds containing (meth)acryloyl groups such as urethane-acrylic, epoxy-acrylic, and various (meth)acrylate-based polymers, particularly polyfunctional compounds containing three or more (meth)acryloyl groups. A high molecular compound etc. are mentioned. In the present invention, among these polymer compounds, polymer compounds containing (meth)acryloyl groups are preferred.

As the polymer compound containing the (meth)acryloyl group, commercially available products can be suitably used. 8KX-128, 8KX-012C, 8KX-014C, 8KX-018C, 8KX-052C, 8KQ-2001, 8BR-600, 8UH-1006, 8UH-1012 (all of these are Taisei Fine Chemical Co., Ltd.); SMP-220A, SMP-250A, SMP-360A, and SMP-550A (all of which are manufactured by Kyoeisha Chemical Co., Ltd.).

The content of component (B) is preferably 1 to 100 parts by mass, more preferably 2 to 50 parts by mass, per 100 parts by mass of the polymer of component (A). When the content of component (B) is within the above range, a release layer resin composition having high heat resistance and appropriate release properties can be obtained. If the content of the cross-linking agent is too small, the solvent resistance and heat resistance of the release layer may be lowered, and the releasability may be lowered. On the other hand, if the content is excessively high, the cross-linking reaction with the resin substrate or the like on the release layer may proceed and the release property may deteriorate. (B) The crosslinking agent may be used singly or in combination of two or more.

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

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

Furthermore, an acidic compound may be added together with the Michael addition reaction catalyst for the purpose of enhancing storage stability during storage. Especially when using a strong base compound with high catalytic activity, the addition of an acidic compound is effective in enhancing the storage stability. Examples of acidic compounds 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.

In the present invention, among these Michael addition reaction catalysts, quaternary ammonium carbonate, quaternary ammonium hydroxide, and tertiary amine are more preferable from the viewpoint of reactivity and storage stability.

The content of component (C) is preferably 0.1 to 20 parts by mass, more preferably 0.1 to 15 parts by mass, per 100 parts by mass of the polymer of component (A). When the content of component (C) 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. (C) A crosslinking catalyst may be used individually by 1 type, and may be used in combination of 2 or more types.

[4] Other Additives The composition for forming a release layer of the present invention may contain a surfactant, if necessary. By adding a surfactant, it is possible to improve the coatability of the release layer forming composition on the substrate. As the surfactant, known surfactants such as nonionic surfactants, fluorine-based surfactants, and silicone-based surfactants can be used.

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 octyl; polyoxyethylene alkylaryl ethers such as phenyl ether and polyoxyethylene nonylphenyl ether; polyoxyethylene/polyoxypropylene block copolymers; sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, Sorbitan fatty acid esters such as sorbitan trioleate and sorbitan tristearate; polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, polyoxyethylene sorbitan Examples include polyoxyethylene sorbitan fatty acid esters such as tristearate.

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

Examples of silicone-based surfactants include organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.).

These surfactants may be used singly or in combination of two or more. When a surfactant is used, the amount used is preferably 0.0001 to 1 part by mass, more preferably 0.001 to 0.5 part by mass, per 100 parts by mass of the polymer (A).

In addition, the composition for forming a release layer of the embodiment of the present invention may contain other additives such as silane coupling agents, rheology modifiers, pigments, dyes, storage stabilizers, antiseptics, as long as they do not impair the effects of the present invention. Foaming agents, antioxidants and the like can be included.

[5] Solvent The release layer-forming composition of the present invention may contain a solvent.
The type and structure of the solvent are particularly limited as long as it is capable of dissolving the components (A), (B), (C), and other additives used as necessary. In the present invention, a glycol ether solvent having 3 to 20 carbon atoms, an ester solvent having 3 to 20 carbon atoms, a ketone solvent having 3 to 20 carbon atoms, and an amide solvent are preferable.

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 ester solvents include ethyl lactate, γ-butyrolactone, methyl 2-hydroxyisobutyrate, and ethyl 2-hydroxyisobutyrate.
Specific examples of ketone-based solvents include methyl ethyl ketone, cyclohexanone, cyclopentanone, and benzophenone.
Specific examples of amide solvents include N-methylpyrrolidone, N,N-dimethylacetamide, 3-methoxy-N,N-dimethylpropanamide and the like.
In addition, a solvent may be used individually by 1 type, and may mix and use 2 or more types.

The content of the solvent is preferably such that the solid concentration in the release layer-forming composition of the present invention becomes 0.1 to 40% by mass, more preferably 0.5 to 20% by mass. An amount of 0.5 to 10% by weight is even more preferred. The solid content is a general term for all components of the release layer-forming composition other than the solvent.

The method for preparing the release layer-forming composition of the present invention is not particularly limited. Examples include a method of mixing agents and the like in a predetermined ratio to form a uniform solution, and a method of adding and mixing other additives as necessary in an appropriate stage of the above preparation method.
The prepared solution of the composition for forming a release layer is preferably used after being filtered using a filter having a pore size of about 0.2 μm.

The viscosity of the release layer-forming composition of the present invention is appropriately set in consideration of the thickness of the release layer to be produced, etc. In particular, it is desirable to obtain a film having a thickness of about 0.01 to 5 μm with good reproducibility. , the viscosity at 25° C. is preferably about 1 to 5,000 mPa·s, more preferably about 1 to 2,000 mPa·s.

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

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

A preferred example of the heating mode in the present invention includes heating at 50 to 150° C. for 1 minute to 1 hour and then increasing the heating temperature as it is to heat at 100 to 280° C. for 5 minutes to 4 hours. In particular, a more preferable example of the heating mode includes heating at 50 to 150° C. for 1 minute to 1 hour and heating at 150 to 280° C. for 5 minutes to 2 hours. Furthermore, another more preferred heating mode is a mode of heating at 50 to 150° C. for 1 minute to 30 minutes and then heating at 200 to 280° C. for 5 minutes to 1 hour.

When the release layer of the present invention is formed on a substrate, the release layer may be formed on a part of the surface of the substrate, or may be formed on the entire surface. Examples of forming the release layer on a part of the surface of the substrate include forming the release layer only on a predetermined area of the surface of the substrate, and forming the release layer on the entire surface of the substrate in a pattern such as a dot pattern or a line and space pattern. There is an aspect of forming.
In the present invention, the term "substrate" means a substrate whose surface is coated with the release layer-forming composition of the present invention, and which is used in the production of flexible electronic devices and the like.

Examples of the substrate (substrate) include glass, metal (silicon wafer, etc.), slate, and the like. Glass is preferred because it has The substrate surface may be composed of a single material, or may be composed of two or more materials. Examples of embodiments in which the surface of the substrate is composed of two or more materials include an embodiment in which a certain area of the surface of the substrate is composed of a certain material and the rest of the surface is composed of another material; , a patterned material such as a line-and-space pattern exists in another material.

The coating method is not particularly limited. screen printing, etc.).

Equipment used for heating includes, for example, a hot plate and an oven. The heating atmosphere may be under air or under an inert gas, and may be under normal pressure or under reduced pressure.

The thickness of the release layer is usually about 0.01 to 50 μm, preferably about 0.01 to 20 μm, more preferably about 0.01 to 5 μm from the viewpoint of productivity. to achieve the desired thickness.

The release layer of the present invention has good releasability from the resin substrate provided thereon. Therefore, the release layer of the present invention can be used to separate the resin substrate of the device from the substrate together with the circuit or the like formed on the resin substrate without damaging the resin substrate of the device in the manufacturing process of the flexible electronic device. It can be suitably used to allow

An example of a method for manufacturing a flexible electronic device using the release layer of the present invention will be described. First, using the composition for forming a release layer of the present invention, a release layer is formed on a glass substrate by the method described above. A resin substrate-forming solution for forming a resin substrate is applied onto the release layer, and the resulting coating film is baked to obtain a resin fixed to the glass substrate via the release layer of the present invention. forming a substrate;

The firing temperature of the coating film is appropriately set according to the type of resin and the like. It is more preferable to set the temperature to 220 to 240°C. By setting the maximum baking temperature in this range for the production of the resin substrate, it is possible to further improve the releasability between the release layer and the resin substrate. Also in this case, as long as the maximum temperature falls within the above range, a step of firing at a temperature lower than that may be included.

It is preferable that the resin substrate is formed so as to cover the entire peeling layer so that the resin substrate has an area larger than that of the peeling 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, a resin substrate made of a cycloolefin polymer, and the like. A method for forming the resin substrate may follow a conventional method. Moreover, it is preferable that the resin substrate has a light transmittance of 80% or more at a wavelength of 400 nm.

Next, on the resin substrate fixed to the substrate via the release layer of the present invention, a desired circuit is formed as necessary, and then, for example, the resin substrate is cut along the release layer to form the circuit. At the same time, the resin substrate is separated from the release layer to separate the resin substrate and the base. At this time, 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 separated from the release layer with a release force of 0.4 N/25 mm or less.

Hereinafter, the present invention will be described in more detail with reference to Synthesis Examples, Preparation Examples, Examples and Comparative Examples, but the present invention is not limited to the following Examples.

Abbreviations used in the following examples have the following meanings.

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

〔solvent〕
CHN: cyclohexanone

[(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.)

[(C) Component]
U-CAT: triethylmonomethylammonium 2-ethylhexanoate (U-CAT18X, manufactured by San-Apro Co., Ltd.)

[Measurement of molecular weight of polymer]
The molecular weights of the acrylic copolymers in the polymerization examples are as follows using Shodex Co., Ltd. room temperature gel permeation chromatography (GPC) apparatus (GPC-101) and Shodex columns (KD-803, KD-805). and measured.
The number average molecular weight (hereinafter referred to as Mn) and weight average molecular weight (hereinafter referred to as Mw) below are expressed in terms of polystyrene.
Column temperature: 40°C
Eluent: Tetrahydrofuran Flow rate: 1.0 mL/min. Standard sample for creating a calibration curve: Standard polystyrene manufactured by Showa Denko Co., Ltd. )

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

[Synthesis Examples 2 to 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 the raw material compounds were as shown in Table 1 below. Table 1 shows the Mw of the obtained polymer.

(2) Preparation of resin substrate-forming composition [Preparation Example 1]
10 g of Zeonor (registered trademark) 1020R (a cycloolefin polymer manufactured by Nippon Zeon Co., Ltd.) 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. This solution was dissolved by stirring for 24 hours in a nitrogen atmosphere to prepare a resin substrate-forming composition F1.

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

[Examples 1-2 to 1-10, Comparative Examples 1-1 to 1-2]
Release layer-forming compositions (A-2) to (A-12) were prepared in the same manner as in Example 1-1, except that the types and amounts of each component were as shown in Table 2. .

(3) Production of release layer and resin substrate [Example 2-1]
Using a spin coater (conditions: 2,000 rpm for about 30 seconds), the release layer forming composition (A-1) was coated on a glass substrate (Corning Eagle XG, 100 mm × 100 mm × 0.7 mm) as a substrate. , hereinafter the same). The obtained 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 having a thickness of about 0.1 μm on the glass substrate. , a glass substrate with a release layer was obtained.
After that, using a spin coater (conditions: 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 is heated using a hot plate at 80° C. for 2 minutes, and then heated at 230° C. for 30 minutes using a hot plate to form a resin substrate having a thickness of about 3 μm on the release layer, A glass substrate with a resin substrate and a release layer was obtained.

[Examples 2-2 to 2-10, Comparative Examples 2-1 to 2-2]
Except for using (A-2) to (A-12) as the release layer forming compositions, the same operations as in Example 2-1 were carried out, Examples 2-2 to 2-10, Comparative Examples 2-1 to A glass substrate with a resin substrate and a release layer of 2-2 was obtained.

[Evaluation of Peeling Force]
The obtained resin substrate/glass substrate with a peeling layer was cut into strips of 25 mm×50 mm using a cutter. Furthermore, after applying Cellotape (registered trademark) (CT-24 manufactured by Nichiban Co., Ltd.), Autograph AGS-X500N (manufactured by Shimadzu Corporation) was used at a peeling angle of 90 ° and a peeling speed of 300 mm / min. It was peeled off and the peel force was measured. In addition, what could not be peeled was made into non-peelable. The evaluation result is "peeling force", and the results are summarized in Table 3.

[Evaluation of peeling interface]
The film thickness of the peeling layer remaining on the glass substrate after evaluation of the peeling force was measured with a stylus type film thickness meter. The film thickness at the time of forming the peeling layer was compared to determine the peeling interface. The evaluation result is the "peeling interface", and if the residual film rate (remaining film rate (%) = peeling layer thickness after peeling / peeling layer thickness at the time of peeling layer formation × 100) is 90% or more, the peeling layer / The resin interface, the cohesive failure of the peeling layer when it is 10% or more and less than 90%, and the glass substrate/peeling layer interface when it is less than 10%. The evaluation results are summarized in Table 3.

From the results shown in Table 3, it was confirmed that the peeling layers of Examples exhibit low peeling force and are excellent in peelability. Moreover, it was confirmed that the release layer of the example was released at the interface between the release layer and the resin substrate. On the other hand, it can be seen that the films of Comparative Examples 2-1 and 2-2 do not function as release layers.

Claims (11)

(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 cross-linking agent having a Michael acceptor group, and (C) a Michael addition reaction catalyst,
A composition for forming a release layer containing (A) The polymer is 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. 2. The composition for forming a release layer according to claim 1, which is a polymer containing 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 (A) the monomer having no Michael donor group in the polymer 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 claims 1 to 4, wherein the Michael acceptor group of the cross-linking agent (B) is a (meth)acryloyl group. The release layer-forming resin composition according to any one of claims 1 to 5, wherein the content of (B) the cross-linking agent is 1 to 100 parts by mass with respect to 100 parts by mass of the polymer (A). 7. The release layer-forming resin composition according to any one of claims 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). A release layer obtained from the release layer-forming composition according to any one of claims 1 to 7. 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 according to claim 8 . 10. The laminate according to claim 9, wherein the resin substrate is a thermosetting film containing an epoxy compound. 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;
Manufacture of a resin substrate, comprising the steps of: forming a resin substrate having a light transmittance of 80% or more at a wavelength of 400 nm on the peeling layer; and peeling the resin substrate with a peeling force of 0.4 N/25 mm or less. Method.