WO2020158521A1

WO2020158521A1 - Composition for forming release layer for slit die coating, and release layer

Info

Publication number: WO2020158521A1
Application number: PCT/JP2020/002014
Authority: WO
Inventors: 和也進藤; 江原　和也
Original assignee: 日産化学株式会社
Priority date: 2019-01-28
Filing date: 2020-01-22
Publication date: 2020-08-06
Also published as: JP7459802B2; KR20210121104A; CN113365742A; CN113365742B; JPWO2020158521A1; TW202045587A

Abstract

The present invention provides a composition for forming a release layer for slit die coating, which contains (A) a polyurea that contains a repeating unit represented by formula (1), (B) an acid compound or a salt thereof, (C) a crosslinking agent that is selected from among compounds having nitrogen atoms which are substituted by a hydroxyalkyl group and/or an alkoxymethyl group, (D) a polymer additive which contains a repeating unit represented by formula (a1), a repeating unit represented by formula (b) and a repeating unit represented by formula (c), and (E) a solvent that contains at least one solvent which has a vapor pressure of 800 Pa or less at 20°C; and this composition is configured such that 3-100 parts by mass of the polymer additive (D) is contained per 100 parts by mass of the polyurea (A).

Description

Composition for forming release layer for slit die coat and release layer

The present invention relates to a release layer forming composition for a slit die coat and a release layer.

In recent years, electronic devices have been required to have the function of being bendable in addition to the characteristics of being thin and lightweight. For this reason, it is required to use a lightweight flexible plastic substrate in place of the conventional glass substrate which is heavy and fragile and cannot be bent.

In particular, for new-generation displays, it is required to develop an active matrix full-color TFT display panel that uses a lightweight flexible plastic substrate (hereinafter also referred to as a resin substrate). In addition, for the touch panel type display, a material corresponding to flexibility, such as a transparent electrode and a resin substrate of a touch panel used in combination with a display panel, has been developed. As the transparent electrode, other transparent electrode materials such as a transparent conductive polymer that can be bent such as PEDOT, metal nanowires and a mixed system thereof have been proposed as the transparent electrode (Patent Documents 1 to 4). ..

On the other hand, the base material of the touch panel film is also made of glass or a sheet made of plastic such as polyethylene terephthalate (PET), polyimide, cycloolefin, or acrylic, and a transparent flexible touch screen panel having flexibility has been developed ( Patent Documents 5 to 7).

Generally, in a flexible touch screen panel, in order to stably perform production and peeling, a peeling layer (adhesive layer) is formed on a supporting substrate such as a glass substrate, a device is formed on the peeling layer, and then peeling is performed. Is manufactured in Japan (Patent Document 8). This peeling layer must not be peeled from the supporting substrate during the process, but a low peeling force is required when peeling.

In addition, in recent years, the slit die coating method has been used in the production line from the viewpoints of the suppression of use of the coating liquid and the productivity accompanying the simplification of the process (Patent Documents 9 and 10). This method, unlike the spin coating method, contains a large number of solvents after film formation, and thus requires a vacuum drying process. This process is carried out between the coating treatment and the heat treatment, and is essential for stabilizing the unstable film immediately after coating. However, since uneven coating occurs due to the influence of the residual solvent due to the reduced pressure, it was necessary to improve this uneven coating.

International Publication No. 2012/147235 JP, 2009-283410, A Japanese Patent Publication No. 2010-507199 JP, 2009-205924, A International Publication No. 2017/002664 International Publication No. 2016/160338 JP, 2005-166145, A Japanese Patent Laid-Open No. 2016-531358 JP, 2014-102490, A Japanese Patent Laid-Open No. 2014-106956

The present invention has been made in view of the above circumstances, even when applied by the slit die coating method, coating unevenness does not occur, excellent adhesion with the substrate, moderate adhesion with the resin substrate and appropriate An object of the present invention is to provide a composition for forming a release layer for slit die coating, which can provide a release layer having a release property.

The present inventors have conducted extensive studies to achieve the above-mentioned object, and as a result, (A) polyurea containing a predetermined repeating unit, (B) an acid compound or a salt thereof, (C) a hydroxyalkyl group and/or an alkoxy. Contains a cross-linking agent selected from compounds having a nitrogen atom substituted with a methyl group, (D) a polymer additive containing a predetermined repeating unit, and (E) a solvent having a vapor pressure at 20° C. of 800 Pa or less. The composition for forming a release layer is excellent as a composition for slit die coating, and it is possible to give a release layer having excellent adhesion to a substrate, appropriate adhesion to a resin substrate and release property with good reproducibility. Heading, the present invention was completed.

That is, the present invention provides the following composition for forming a release layer for slit die coating and a release layer.
1. (A) a polyurea containing a repeating unit represented by the following formula (1),
(B) an acid compound or a salt thereof,
(C) a cross-linking agent selected from compounds having a nitrogen atom substituted with a hydroxyalkyl group and/or an alkoxymethyl group,
(D) A polymer additive containing a repeating unit represented by the following formula (a1), a repeating unit represented by the following formula (b) and a repeating unit represented by the following formula (c), and (E) 20 Including a solvent containing at least one solvent having a vapor pressure at 800° C. of 800 Pa or less,
A composition for forming a release layer for a slit die coat, wherein the polymer additive (D) is contained in an amount of 3 to 100 parts by mass relative to 100 parts by mass of the polyurea (A).

[In the formula, A ¹ , A ² , A ³ , A ⁴ , A ⁵ and A ⁶ are each independently a hydrogen atom, a methyl group or an ethyl group,
X ¹ is a group represented by the following formula (1-1), (1-2), (1-3) or (1-4),

(In the formula, R ¹ and R ² are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 3 to 6 carbon atoms, a benzyl group or a phenyl group, and the phenyl group is a carbon atom. Substituted with at least one group selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, a halogen atom, an alkoxy group having 1 to 6 carbon atoms, a nitro group, a cyano group, a hydroxy group and an alkylthio group having 1 to 6 carbon atoms. R ¹ and R ² may combine with each other to form a ring having 3 to 6 carbon atoms together with the carbon atom to which they are bonded, and R ³ has 1 to 6 carbon atoms. An alkyl group, an alkenyl group having 3 to 6 carbon atoms, a benzyl group or a phenyl group, wherein the phenyl group is an alkyl group having 1 to 6 carbon atoms, a halogen atom, an alkoxy group having 1 to 6 carbon atoms, a nitro group, cyano May be substituted with at least one group selected from the group consisting of a group, a hydroxy group and an alkylthio group having 1 to 6 carbon atoms.)
Q ¹ is a group represented by the following formula (1-5) or (1-6).

(In the formula, X ² is a group represented by the formula (1-1), the formula (1-2) or the formula (1-4), and Q ² is an alkylene group having 1 to 10 carbon atoms, or phenylene. Group, naphthylene group or anthrylene group, wherein the phenylene group, naphthylene group and anthrylene group are an alkyl group having 1 to 6 carbon atoms, a halogen atom, an alkoxy group having 1 to 6 carbon atoms, a nitro group, a cyano group, a hydroxy group. , And at least one group selected from the group consisting of alkylthio groups having 1 to 6 carbon atoms, and n ¹ and n ² are each independently 0 or 1.)]

(In the formula, R ^A is each independently a hydrogen atom or a methyl group, and R ^B1 is a branched alkyl group having 3 or 4 carbon atoms in which at least one hydrogen atom is substituted with a fluorine atom, R ^C is a hydroxyalkyl group having 1 to 10 carbon atoms, and R ^D is a polycyclic alkyl group having 6 to 20 carbon atoms or an aryl group having 6 to 12 carbon atoms.)
2. (D) In the repeating unit represented by the formula (b) of the polymer additive, R ^C is a hydroxyalkyl group having 2 to 10 carbon atoms, and the carbon atom to which the hydroxy group is bonded is a secondary carbon atom. And the content of the repeating unit represented by the formula (a1) is 30 mol% or more based on all repeating units of the polymer additive (D).
3. The composition for forming a release layer for slit die coating according to 1 or 2, wherein X ¹ is a group represented by formula (1-3).
4. The composition for forming a release layer for slit die coating according to 3, wherein R ³ is a 2-propenyl group.
5. The composition for forming a release layer for slit die coating according to any one of 1 to 4, wherein Q ¹ is a group represented by the formula (1-5).
6. The composition for forming a release layer for slit die coating according to any one of 1 to 5, wherein the component (B) is a sulfonic acid compound or a salt thereof.
7. The composition for forming a release layer for slit die coat according to any one of 1 to 6, wherein the crosslinking agent (C) is a compound represented by any of the following formulas (C-1) to (C-7).

(In the formula, R ¹¹ to R ³⁸ are each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and R ³⁹ is a hydrogen atom or a methyl group.)
8. The composition for forming a release layer for slit die coating according to any one of 1 to 7, wherein the content of the cross-linking agent (C) is 10 to 100 parts by mass relative to 100 parts by mass of (A) polyurea.
9. A release layer obtained from the composition for forming a release layer for slit die coating according to any one of 1 to 8.
A laminate in which a resin layer having a light transmittance at a wavelength of 400 nm of 80% or more is laminated on a release layer of 10.9.
A step of applying a release layer-forming composition for slit die coating according to any one of 11.1 to 8 to a substrate to form a release layer;
Manufacture of a resin substrate including a step of forming a resin substrate having a light transmittance of 400% at a wavelength of 400% or more on the peeling layer, and peeling the resin substrate with a peeling force of 0.15 N/25 mm or less Method.

By using the composition for forming a release layer for slit die coating of the present invention, coating unevenness does not occur, excellent adhesion to the substrate, a suitable adhesion to the resin substrate and a release layer having a suitable releasability. It can be obtained with good reproducibility. Further, in the process of manufacturing a flexible electronic device, it is possible to separate the resin substrate from the base body together with the circuit and the like without damaging the resin substrate formed on the base body or a circuit or the like provided thereon. It will be possible. Therefore, the composition for forming a release layer for a slit die coat of the present invention can contribute to speeding up the manufacturing process of a flexible electronic device including a resin substrate, improving its yield, and the like.

[Release layer forming composition for slit die coat]
The composition for forming a release layer for slit die coating of the present invention is substituted with (A) a polyurea containing a predetermined repeating unit, (B) an acid compound or a salt thereof, (C) a hydroxyalkyl group and/or an alkoxymethyl group. It contains a crosslinking agent selected from compounds having a nitrogen atom, (D) a polymer additive containing a predetermined repeating unit, and (E) a solvent.

[(A) Polyurea]
The polyurea as the component (A) contains a repeating unit represented by the following formula (1).

In the formula (1), A ¹ , A ² , A ³ , A ⁴ , A ⁵ and A ⁶ are each independently a hydrogen atom, a methyl group or an ethyl group, but from the viewpoint of releasability and productivity, All of A ¹ to A ⁶ are preferably hydrogen atoms.

In the formula (1), X ¹ is a group represented by the following formula (1-1), (1-2), (1-3) or (1-4).

In formulas (1-1) and (1-2), R ¹ and R ² are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 3 to 6 carbon atoms, a benzyl group or phenyl. The phenyl group is a group consisting of an alkyl group having 1 to 6 carbon atoms, a halogen atom, an alkoxy group having 1 to 6 carbon atoms, a nitro group, a cyano group, a hydroxy group and an alkylthio group having 1 to 6 carbon atoms. It may be substituted with at least one group selected from the following, and R ¹ and R ² may be bonded to each other to form a ring having 3 to 6 carbon atoms together with the carbon atom to which they are bonded.

In the formula (1-3), R ³ is an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 3 to 6 carbon atoms, a benzyl group or a phenyl group, and the phenyl group is an alkyl group having 1 to 6 carbon atoms. It may be substituted with at least one group selected from the group consisting of a group, a halogen atom, an alkoxy group having 1 to 6 carbon atoms, a nitro group, a cyano group, a hydroxy group and an alkylthio group having 1 to 6 carbon atoms.

In the formula (1), Q ¹ is a group represented by the following formula (1-5) or (1-6).

In formula (1-5), X ² is a group represented by formula (1-1), formula (1-2) or formula (1-4). In the formula (1-5), for example, when X ² is a group represented by the formula (1-2), its structure is represented by the following formula (1-5-1).

(In the formula, R ¹ and R ² are the same as above.)

In the formula (1-6), Q ² is an alkylene group having 1 to 10 carbon atoms, a phenylene group, a naphthylene group or an anthrylene group. The phenylene group, naphthylene group and anthrylene group include an alkyl group having 1 to 6 carbon atoms, a halogen atom, an alkoxy group having 1 to 6 carbon atoms, a nitro group, a cyano group, a hydroxy group and an alkylthio group having 1 to 6 carbon atoms. It may be substituted with at least one group selected from the group consisting of Further, when Q ² is a phenylene group, a naphthylene group or an anthrylene group, the position of their bond is not particularly limited. That is, for example, when the phenylene group is bonded at the 1-position and 2-position, when it is bonded at the 1-position and 3-position, or when it is bonded at the 1-position and 4-position, the naphthylene group is 1 When bonded at position 2 and position, bonded at position 1 and position 4, bonded at position 1 and position 5 or bonded at position 2 and position 3, the anthrylene group is There may be a bond at the 1-position and the 2-position, a bond at the 1-position and the 4-position, a bond at the 9-position and the 10-position, etc.

The alkyl group having 1 to 6 carbon atoms may be linear, branched or cyclic, and examples thereof include a methyl group, an ethyl group, an isopropyl group, an n-butyl group and a cyclohexyl group. The alkenyl group having 3 to 6 carbon atoms may be linear, branched or cyclic, and examples thereof include a 2-propenyl group and a 3-butenyl group.

The alkoxy group having 1 to 6 carbon atoms may be linear, branched or cyclic, and examples thereof include a methoxy group, an ethoxy group, an isopropoxy group, an n-pentyloxy group and a cyclohexyloxy group. .. The alkylthio group having 1 to 6 carbon atoms may be linear, branched or cyclic, and examples thereof include a methylthio group, an ethylthio group, an isopropylthio group, an n-pentylthio group and a cyclohexylthio group. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Further, examples of the ring having 3 to 6 carbon atoms formed by combining R ¹ and R ² include a cyclobutane ring, a cyclopentane ring, a cyclohexane ring and the like.

The alkylene group having 1 to 10 carbon atoms may be linear, branched or cyclic and includes, for example, methylene group, ethylene group, propylene group, pentamethylene group, cyclohexylene group, 2-methylpropylene group and the like. Are listed.

In the formula (1), when X ¹ is a group represented by the formula (1-2), the structure is represented by the following formula (2), and X ¹ is the formula (1-3). In the case of the group represented, its structure is represented by the following formula (3). Further, in the formula (3), it is preferable that R ³ is a 2-propenyl group.

(In the formula, A ¹ to A ⁶ , R ¹ to R ³ and Q ¹ are the same as above.)

In the formula (1), Q ¹ preferably contains a cyclic structure from the viewpoint of heat resistance of the polyurea as the component (A). That is, Q ¹ is a group represented by the formula (1-5) or a group represented by the formula (1-6), and Q ² is a cyclic alkylene group, a phenylene group, a naphthylene group or an anthrylene group. Is preferred, and a group represented by formula (1-5) is more preferred.

As the repeating unit represented by the formula (1), those represented by the following formulas (4) to (22) are preferable. In the formula below, Me is a methyl group and Et is an ethyl group.

The component (A) polyurea can be synthesized with reference to, for example, International Publication No. 2005/098542.

The weight average molecular weight (Mw) of (A) polyurea is preferably from 1,000 to 200,000, more preferably from 3,000 to 100,000, even more preferably from 4,000 to 30,000, and from 5,000 to 20,000 is more preferable. The dispersity (Mw/Mn) thereof is preferably 1.3 to 4.0, more preferably 1.4 to 2.5. In addition, Mn is a number average molecular weight and Mw and Mn are polystyrene conversion measurement values by gel permeation chromatography (GPC).

[(B) Acid compound or salt thereof]
The composition for forming a release layer of the present invention contains an acid compound or a salt thereof as the component (B). Examples of the acid compound include p-toluenesulfonic acid, trifluoromethanesulfonic acid, pyridinium-p-toluenesulfonate, salicylic acid, camphorsulfonic acid, sulfosalicylic acid, 4-chlorobenzenesulfonic acid, 4-hydroxybenzenesulfonic acid, benzenedisulfonic acid, Examples thereof include sulfonic acid compounds such as 1-naphthalene sulfonic acid, and carboxylic acid compounds such as salicylic acid, sulfosalicylic acid, citric acid, benzoic acid, and hydroxybenzoic acid. Examples of the salt of the acid compound include pyridinium salt, isopropanolamine salt, N-methylmorpholine salt and the like of the acid, and specific examples thereof include pyridinium p-toluenesulfonate, pyridinium 1-naphthalenesulfonate, and isopropanol. Examples thereof include amine p-toluene sulfonate and N-methylmorpholine p-toluene sulfonate.

The content of the component (B) is preferably 0.01 to 30 parts by mass, and more preferably 0.1 to 20 parts by mass, relative to 100 parts by mass of the polyurea of the component (A). When the content of the component (B) is within the above range, it is possible to obtain a composition which has a high heat resistance and an appropriate peeling property and can give a peeling layer having excellent stability after film formation. The acid compound (B) or a salt thereof may be used alone or in combination of two or more.

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

As the crosslinking agent, compounds represented by any of the following formulas (C-1) to (C-7) are preferable.

In the formula, R ¹¹ to R ³⁸ are each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, preferably an alkyl group having 1 to 6 carbon atoms. R ³⁹ is a hydrogen atom or a methyl group.

Specific examples of the cross-linking agent include hexamethylolmelamine, tetramethylolbenzoguanamine, 1,3,4,6-tetramethylolglycoluril, hexamethoxymethylmelamine, tetramethoxymethylbenzoguanamine, 1,3,4,6-tetrakis( Examples thereof include nitrogen-containing compounds such as methoxymethyl)glycoluril, 1,3,4,6-tetrakis(butoxymethyl)glycoluril, and 1,3,4,6-tetrakis(hydroxymethyl)glycoluril.

Further, as a cross-linking agent, Ornex Co. methoxymethyl type melamine compound (trade name Cymel (registered trademark) 300, Cymel 301, Cymel 303, Cymel 350), butoxymethyl type melamine compound (trade name Mycoat (registered trademark) 506, Mycoat 508), glycoluril compound (trade name Cymel 1170, POWDERLINK 1174), methylated urea resin (trade name UFR65), butylated urea resin (trade names UFR300, U-VAN10S60, U-VAN10R, U-VAN11HV), Commercially available nitrogen-containing compounds such as urea/formaldehyde resin (trade name: Beckamine (registered trademark) J-300S, Beckamine P-955, Beckamine N) manufactured by DIC Corporation can be used.

In addition, as a cross-linking agent, 3,3'-5,5'-tetrakis(methoxymethyl)-[1,1'-biphenyl]-4,4'-diol, 5,5'-(1-methylethylidene)bis Examples thereof include aromatic ring compounds such as [2-hydroxy-1,3-benzenedimethanol].

Further, as a cross-linking agent, a hydroxymethyl group or an alkoxymethyl group such as N-hydroxymethyl(meth)acrylamide, N-methoxymethyl(meth)acrylamide, N-ethoxymethyl(meth)acrylamide, N-butoxymethyl(meth)acrylamide, etc. A polymer produced using a (meth)acrylamide compound substituted with can be used. Examples of such a polymer include poly(N-butoxymethyl(meth)acrylamide), a copolymer of N-butoxymethyl(meth)acrylamide and styrene, N-hydroxymethyl(meth)acrylamide and methyl(meth). Copolymer with acrylate, Copolymer with N-ethoxymethylmethacrylamide and benzyl methacrylate, Copolymer with N-butoxymethyl (meth)acrylamide, benzyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate, etc. Are listed.

More preferably, the crosslinking agent is hexamethoxymethylmelamine, tetramethoxymethylbenzoguanamine, 1,3,4,6-tetrakis(methoxymethyl)glycoluril (POWDERLINK 1174), 1,3,4,6-tetrakis(butoxymethyl). ) Glycoluril, 1,3,4,6-tetrakis(hydroxymethyl)glycoluril.

These cross-linking agents can cause a cross-linking reaction by self-condensation. Further, it can cause a crosslinking reaction with the hydroxy group in the polyurea as the component (A). Then, by such a crosslinking reaction, the peeling layer formed becomes strong and becomes a peeling layer having low solubility in an organic solvent.

The content of the component (C) is preferably 10 to 100 parts by mass, more preferably 20 to 50 parts by mass, relative to 100 parts by mass of the polyurea of the component (A). When the content of the component (C) is within the above range, a composition having high heat resistance and appropriate peelability and capable of providing a peeling layer having excellent stability after film formation can be obtained. The (C) crosslinking agent may be used alone or in combination of two or more kinds.

[(D) Polymer additive]
The release layer-forming composition of the present invention is represented by the repeating unit represented by the following formula (a1), the repeating unit represented by the following formula (b), and the following formula (c) as the component (D). It includes a polymeric additive containing repeating units.

In the formula, R ^A's are each independently a hydrogen atom or a methyl group. R ^B1 is a branched alkyl group having 3 or 4 carbon atoms in which at least one hydrogen atom is substituted with a fluorine atom. R ^C is a hydroxyalkyl group having 1 to 10 carbon atoms. R ^D is a polycyclic alkyl group having 6 to 20 carbon atoms or an aryl group having 6 to 12 carbon atoms.

Examples of the branched alkyl group having 3 or 4 carbon atoms include isopropyl group, isobutyl group, sec-butyl group and tert-butyl group. R ^B1 is preferably one in which at least one hydrogen atom of these branched alkyl groups is substituted with a fluorine atom, and specific examples include a 1,1,1-trifluoroisopropyl group, 1,1,1, Examples thereof include a 3,3,3-hexafluoroisopropyl group and a nonafluorotert-butyl group.

Examples of the hydroxyalkyl group having 1 to 10 carbon atoms include hydroxymethyl group, 2-hydroxyethyl group, 3-hydroxypropyl group, 4-hydroxybutyl group, 5-hydroxypentyl group, 6-hydroxyhexyl group and 7-hydroxy group. Heptyl group, 8-hydroxyoctyl group, 9-hydroxynonyl group, 10-hydroxydecyl group, 2-hydroxy-1-methylethyl group, 2-hydroxy-1,1-dimethylethyl group, 3-hydroxy-1-methyl Propyl group, 3-hydroxy-2-methylpropyl group, 3-hydroxy-1,1-dimethylpropyl group, 3-hydroxy-1,2-dimethylpropyl group, 3-hydroxy-2,2-dimethylpropyl group, 4 A hydroxyalkyl group having 1 to 10 carbon atoms such as -hydroxy-1-methylbutyl group, 4-hydroxy-2-methylbutyl group, 4-hydroxy-3-methylbutyl group, etc., wherein the carbon atom to which the hydroxy group is bonded is the first Primary carbon atom; 1-hydroxyethyl group, 1-hydroxypropyl group, 2-hydroxypropyl group, 1-hydroxybutyl group, 2-hydroxybutyl group, 1-hydroxyhexyl group, 2-hydroxyhexyl group, 1 -Hydroxyoctyl group, 2-hydroxyoctyl group, 1-hydroxydecyl group, 2-hydroxydecyl group, 1-hydroxy-1-methylethyl group, 2-hydroxy-2-methylpropyl group and the like having 2 to 10 carbon atoms Examples thereof include hydroxyalkyl groups in which the carbon atom to which the hydroxy group is bonded is a secondary or tertiary carbon atom. R ^C is particularly preferably a hydroxyalkyl group having 2 to 10 carbon atoms in which the carbon atom to which the hydroxy group is bonded is a secondary carbon atom.

Examples of the polycyclic alkyl group having 6 to 20 carbon atoms include 1-adamantyl group, 2-adamantyl group, isobornyl group and norbornyl group. Examples of the aryl group having 6 to 12 carbon atoms include phenyl group, 1-naphthyl group, 2-naphthyl group, 1-biphenylyl group and 2-biphenylyl group.

Further, the polymer additive (D) includes a repeating unit represented by the following formula (a2), a repeating unit represented by the following formula (b), a repeating unit represented by the following formula (c), and a following formula ( It may contain a repeating unit represented by d).

In the formula, R ^A , R ^C and R ^D are the same as above. R ^B2 is a branched alkyl group having 3 or 4 carbon atoms in which at least one hydrogen atom is substituted with a fluorine atom (provided that 2-methyl-1,1,1,3,3,3-hexafluoro). Excluding isopropyl group.). Examples of the branched alkyl group having 3 or 4 carbon atoms include the same ones as described above. R ^E is a single bond, a polycyclic alkylene group having 6 to 20 carbon atoms or an arylene group having 6 to 12 carbon atoms. R ^F is a single bond or an alkylene group having 1 to 10 carbon atoms. R ^G is a methyl group, an ethyl group or a hydroxy group.

Examples of the polycyclic alkylene group having 6 to 20 carbon atoms include groups obtained by removing one hydrogen atom from the above-mentioned specific examples of polycyclic alkyl groups having 6 to 20 carbon atoms, and examples thereof include an adamantylene group, Examples thereof include an isobornylene group and a norbornylene group.

Examples of the arylene group having 6 to 12 carbon atoms include a group obtained by removing one hydrogen atom from the specific examples of the aryl group having 6 to 12 carbon atoms described above, and examples thereof include a phenylene group, a naphthylene group and a biphenylylene group. Can be mentioned.

Examples of the alkylene group having 1 to 10 carbon atoms are the same as those exemplified in the description of Q ² . In the present invention, an alkylene group having 1 to 5 carbon atoms is preferable, a methylene group and an ethylene group are more preferable, and a methylene group is even more preferable.

Examples of the repeating unit represented by the formula (a1) or (a2) include, but are not limited to, those represented by the following formulas (a-1) to (a-3). In the formula below, R ^A is the same as above.

Examples of the repeating unit represented by the formula (b) include, but are not limited to, those represented by the following formulas (b-1) to (b-16). In the formula below, R ^A is the same as above.

Examples of the repeating unit represented by the formula (c) include, but are not limited to, those represented by the following formulas (c-1) to (c-13). In the formula below, R ^A is the same as above.

Examples of the repeating unit represented by the formula (d) include, but are not limited to, those represented by the following formulas (d-1) to (d-8). In the formula below, R ^A is the same as above.

The polymer additive (D) contains a repeating unit represented by the formula (a1), a repeating unit represented by the formula (b) and a repeating unit represented by the formula (c), When the carbon atom to which the hydroxy group is bonded in the hydroxyalkyl group in the repeating unit represented by b) is a secondary or tertiary carbon atom, the content of the repeating unit represented by the formula (a1) is In all the repeating units, 30 to 60 mol% is preferable, and 35 to 50 mol% is more preferable. The content of the repeating unit represented by the formula (b) is preferably 10 to 35 mol% and more preferably 15 to 30 mol% in all repeating units. The content of the repeating unit represented by the formula (c) is preferably 5 to 60 mol% and more preferably 20 to 50 mol% in all repeating units.

The polymer additive (D) contains a repeating unit represented by the formula (a1), a repeating unit represented by the formula (b) and a repeating unit represented by the formula (c), When the carbon atom to which the hydroxy group is bonded in the hydroxyalkyl group in the repeating unit represented by b) is a primary carbon atom, the content of the repeating unit represented by the formula (a1) is , 15 to 60 mol% is preferable, 25 to 60 mol% is more preferable, 30 to 60 mol% is much more preferable, and 35 to 50 mol% is further preferable. The content of the repeating unit represented by the formula (b) is preferably from 8 to 38 mol%, more preferably from 10 to 38 mol%, further preferably from 10 to 35 mol%, more preferably from 15 to 30 mol%, based on all repeating units. Is even more preferable. The content of the repeating unit represented by the formula (c) is preferably from 2 to 77 mol%, more preferably from 2 to 65 mol%, even more preferably from 5 to 60 mol%, and further preferably from 20 to 50, based on all repeating units. More preferred is mol %.

(D) The polymer additive is represented by the repeating unit represented by the formula (a2), the repeating unit represented by the formula (b), the repeating unit represented by the formula (c), and the formula (d). When it contains a repeating unit, the content of the repeating unit represented by the formula (a2) is preferably from 2 to 45 mol%, more preferably from 5 to 35 mol%, based on all repeating units. The content of the repeating unit represented by the formula (b) is preferably 20 to 35 mol% and more preferably 25 to 35 mol% in all repeating units. The content of the repeating unit represented by the formula (c) is preferably 30 to 45 mol% and more preferably 35 to 45 mol% in all repeating units. The content of the repeating unit represented by the formula (d) is preferably 5 to 18 mol% and more preferably 5 to 15 mol% in all repeating units.

(D) The Mw of the polymer additive is preferably 2,000 to 10,000, more preferably 3,000 to 8,000. The Mw/Mn thereof is preferably 1.0 to 2.1, more preferably 1.0 to 1.9.

The content of the polymer additive of the component (D) is 3 to 100 parts by mass with respect to 100 parts by mass of the polyurea of the component (A), more preferably 3 to 80 parts by mass, and 3 to 50 parts by mass. Even more preferable. If the content of the polymer additive is less than 3 parts by mass, the peeling force may increase, and if it exceeds 100 parts by mass, it may repel during film formation. The polymer additives (D) may be used alone or in combination of two or more.

[(E) Solvent]
The composition for forming a release layer of the present invention contains a solvent as the component (E). The solvent is preferably a glycol ether solvent having 3 to 20 carbon atoms, an ester solvent having 3 to 20 carbon atoms, a ketone solvent having 3 to 20 carbon atoms, or a cyclic compound solvent having 3 to 20 carbon atoms.

As the glycol ether solvent, propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether, propylene glycol monobutyl ether, ethylene Glycol monomethyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether (Diglyce), diethylene glycol diethyl ether, diethylene glycol monohexyl ether, diethylene glycol butyl methyl ether, triethylene Glycol monomethyl ether, triethylene glycol dimethyl ether (Triglyme), diethylene glycol monobutyl ether, diethylene glycol ethyl methyl ether, diethylene glycol isopropyl methyl ether, diethylene glycol dibutyl ether, dimethoxytetraethylene glycol, dipropylene glycol methyl ether, dipropylene glycol dimethyl ether, dipropylene glycol monomethyl ether Examples thereof include ether, diethylene glycol monoethyl ether acetate (DEGEEA), methoxymethyl butanol, tripropylene glycol dimethyl ether, and triethylene glycol butyl methyl ether.

Examples of the ester solvent include ethyl acetate, butyl acetate, methoxybutyl acetate, amyl acetate, isopropyl acetate, methyl lactate, ethyl lactate (EL), butyl lactate, methyl 2-hydroxyisobutyrate, ethyl 2-hydroxyisobutyrate, and 3 -Ethyl ethoxypropionate and the like can be mentioned.

Examples of the ketone solvent include methyl ethyl ketone, methyl propyl ketone, methyl isobutyl ketone, diisobutyl ketone, diacetone alcohol, cyclohexanone and cyclopentanone.

Examples of the solvent for the cyclic compound include tetrahydrofuran, 1,4-dioxane, 1,3-dioxolane, 2-pyrrolidone, N-methylpyrrolidone (NMP), N-ethylpyrrolidone (NEP) and 1,3-dimethyl-2-imidazo. Examples thereof include ridinone (DMI) and γ-butyrolactone (GBL).

The component (E) solvent contains at least one solvent having a vapor pressure at 20° C. of 800 Pa or less. The vapor pressure of the solvent is preferably 700 Pa or less, more preferably 600 Pa or less, from the viewpoint of volatility during reduced pressure drying. The lower limit of the vapor pressure is not particularly limited, but is usually 0.1 Pa or higher, preferably 0.5 Pa or higher. As the solvent having a vapor pressure of 800 Pa or less, those having a vapor pressure of 800 Pa or less are preferable among the above-mentioned solvents. Examples of such a solvent include PGMEA, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether, ethylene glycol diethyl ether, ethylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether, Diglyme, diethylene glycol diethyl ether, ethylene glycol butyl methyl ether, Triglyme, Diethylene glycol dibutyl ether, diethylene glycol ethyl methyl ether, diethylene glycol isopropyl methyl ether, dimethoxytetraethylene glycol, dipropylene glycol methyl ether, dipropylene glycol dimethyl ether, DEGEEA, methoxymethyl butanol, triethylene glycol butyl methyl ether, EL, butyl lactate, 2- Methyl hydroxyisobutyrate, ethyl 2-hydroxyisobutyrate, ethyl 3-ethoxypropionate, diacetone alcohol, cyclohexanone, 2-pyrrolidone, NMP, NEP, DMI, GBL and the like are preferable.

The content of the solvent having a vapor pressure of 800 Pa or less at 20° C. is preferably 1 to 99.9% by mass, more preferably 1 to 90% by mass in the composition of the present invention from the viewpoint of nonvolatility during drying under reduced pressure. It is more preferably 5 to 80% by mass.

The content of the solvent (E) is preferably such that the solid content concentration in the release layer-forming composition of the present invention is 0.1 to 40% by mass, and more preferably 0.5 to 20% by mass. An amount of 0.5 to 10% by mass is more preferable. In addition, the solid content is a general term for components other than the solvent among all components of the composition for forming a release layer. The solvent may be used alone or in combination of two or more.

[Other additives]
The release layer-forming composition of the present invention may contain a surfactant, if necessary. By adding the surfactant, the coating property of the release layer-forming composition on the substrate can be improved. 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 thereof 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), FLUORAD (registered trademark) FC430, FC431 (manufactured by 3M), Asahi Guard (registered trademark) AG710, Surflon (registered trademark) Examples thereof include S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by Asahi Glass Co., Ltd.).

Also, examples of the silicone-based surfactant include organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.) and the like.

When the composition for forming a release layer contains a surfactant, the content thereof is preferably 0.0001 to 1 part by mass, and 0.001 to 0.5 part by mass, relative to 100 parts by mass of (A) polyurea. More preferable. The surfactants may be used alone or in combination of two or more.

[Preparation of composition for forming release layer for slit die coat]
The method for preparing the composition for forming a release layer for slit die coating of the present invention is not particularly limited. As a preparation method, for example, a solution of the component (A) dissolved in a solvent is mixed with the components (B), (C), (D) and (E) at a predetermined ratio to form a uniform solution. And a method in which other additives are further added and mixed at an appropriate stage of the above-mentioned preparation method, if necessary.

In the preparation of the release layer-forming composition of the present invention, the solution of the specific copolymer (polymer) obtained by the polymerization reaction in the solvent can be used as it is. In this case, for example, the component (A), the component (B), the component (C), the component (D), and the component (E) are added to the solution as described above to form a uniform solution. At this time, a solvent may be additionally added for the purpose of adjusting the concentration. At this time, the solvent used in the production process of the component (A) and the solvent used for adjusting the concentration of the release layer-forming composition may be the same or different.

Also, it is preferable to use the prepared solution of the composition for forming a release layer after filtering it with 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., but in particular, a film having a thickness of about 0.01 to 5 μm can be reproducibly obtained. For the purpose, it is usually about 1 to 5,000 mPa·s at 25° C., preferably about 1 to 2,000 mPa·s.

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

[Peeling layer]
The composition for forming a release layer for slit die coat of the present invention is applied to a substrate by a slit die coater using a slit die coater and then baked at 180 to 250°C. It is possible to obtain a release layer having an adhesiveness, an appropriate adhesiveness with a resin substrate, and an appropriate releasability.

ㆍThe heating time cannot be specified because it depends on the heating temperature, but it is usually 1 minute to 5 hours. Further, the firing temperature may include a step of firing at a temperature lower than the maximum temperature as long as it falls within the above range.

A preferable example of the heating mode in the present invention is a mode in which after heating at 50 to 150° C. for 1 minute to 1 hour, the heating temperature is raised as it is and heating at 180 to 250° C. for 5 minutes to 4 hours. In particular, a more preferable example of the heating mode is a mode in which heating is performed at 50 to 150° C. for 1 minute to 1 hour, and heating is performed at 200 to 250° C. for 5 minutes to 2 hours. Further, as another more preferable example of the heating mode, there is a mode of heating at 50 to 150° C. for 1 to 30 minutes and then heating at 200 to 250° 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 partial surface of the substrate or may be formed on the entire surface. The mode of forming the release layer on a part of the surface of the substrate is such that the release layer is formed only in a predetermined range on the surface of the substrate, or the release layer is formed in a pattern such as a dot pattern or a line and space pattern on the entire surface of the substrate. There is a mode of forming the like. In addition, in the present invention, the substrate means a substrate whose surface is coated with the composition for forming a release layer, which is used for manufacturing a flexible electronic device or the like.

Examples of the substrate (substrate) include glass, metal (silicon wafer, etc.), slate, and the like. In particular, the release layer obtained from the release layer-forming composition of the present invention has sufficient adhesion to it. Glass is preferable because it has. The surface of the substrate may be made of a single material or may be made of two or more materials. As a mode in which the substrate surface is composed of two or more materials, a certain range of the substrate surface is composed of a certain material, and the remaining surface is composed of another material. , A pattern-like material such as a line-and-space pattern exists in another material.

Examples of equipment used for heating include hot plates and ovens. 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, and the thickness of the coating film before heating. To achieve the desired thickness.

The release layer of the present invention has excellent adhesion to a substrate, particularly a glass substrate, and appropriate adhesion to a resin substrate and appropriate release properties. Therefore, the peeling layer of the present invention is used for peeling the resin substrate together with the circuit and the like formed on the resin substrate from the substrate in the manufacturing process of the flexible electronic device without damaging the resin substrate of the device. Can be suitably used.

[Method of manufacturing resin substrate]
An example of a method for manufacturing a flexible electronic device using the release layer of the present invention will be described. First, the composition for forming a release layer for slit die coating of the present invention is used to form a release layer on a glass substrate by the method described above. A resin substrate fixed on a glass substrate via the release layer of the present invention by applying a resin substrate forming solution for forming a resin substrate on the release layer and baking the resulting coating film. To form.

The baking temperature of the coating film is appropriately set according to the type of resin, etc., but in the present invention, the maximum temperature during baking is preferably 200 to 250° C., and 210 to 250° C. It is more preferable that the temperature is 220 to 240° C. By setting the maximum temperature during firing during the production of the resin substrate within this range, the adhesiveness between the base release layer and the substrate, and the appropriate adhesiveness and release property between the release layer and the resin substrate are further improved. be able to. Also in this case, as long as the maximum temperature falls within the above range, a step of firing at a temperature below that may be included.

-The resin substrate covers the release layer entirely, and the resin substrate is formed in an area larger than the area of the release layer. Examples of the resin substrate include a resin substrate made of an acrylic polymer and a resin substrate made of a cycloolefin polymer. The resin substrate may be formed by a conventional method. The resin substrate preferably has a light transmittance of 80% or more at a wavelength of 400 nm.

Next, a desired circuit is formed, if necessary, on the resin substrate fixed to the substrate via the release layer of the present invention, and then the resin substrate is cut along the release layer, for example. At the same time, the resin substrate is separated from the release layer to separate the resin substrate and the base body. At this time, a part of the substrate may be cut together with the release layer. When the release layer of the present invention is used, the resin substrate can be released from the release layer with a release force of 0.15 N/25 mm or less, particularly 0.1 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.

The compounds used in the following examples are as follows. The vapor pressure is the value at 20°C.
PGME: Propylene glycol monomethyl ether (vapor pressure 1200 Pa)
PGMEA: Propylene glycol monomethyl ether acetate (vapor pressure 500 Pa)
EL: Ethyl lactate (vapor pressure 279 Pa)
GBL: γ-butyrolactone (vapor pressure 150 Pa)
DEGEEA: Diethylene glycol monoethyl ether acetate (vapor pressure 6 Pa)
Triglyme: Triethylene glycol dimethyl ether (vapor pressure 120 Pa)
Diglyme: Diethylene glycol dimethyl ether (vapor pressure 330 Pa)
PL-LI: 1,3,4,6-tetrakis(methoxyethyl)glycoluril (manufactured by Ornex, trade name: POWDERLINK 1174)
PPTS: pyridinium p-toluenesulfonate IBXA: isobornyl methacrylate HPMA: 2-hydroxypropyl methacrylate ADMA: 2-adamantyl methacrylate HFiPMA: 1,1,1,3,3,3-hexafluoroisopropyl methacrylate AIBN:azo Bisisobutyronitrile

Further, the weight average molecular weight (Mw) of the polymer is measured by a GPC device manufactured by JASCO Corporation (column: Shodex (registered trademark) KD801 and KD805 (manufactured by Showa Denko KK); eluent: dimethylformamide/LiBr. H ₂ O (29.6 mM)/H ₃ PO ₄ (29.6 mM)/THF (0.1% by mass); flow rate: 1.0 mL/min; column temperature: 40° C.; Mw: standard polystyrene conversion value) It was done using.

[1] Synthesis of Polymer [Synthesis Example 1] Synthesis of Polyurea (L1) 100 g of monoallyl diglycidyl isocyanuric acid (manufactured by Shikoku Chemicals Co., Ltd.), 66.4 g of 5,5-diethylbarbituric acid and benzyltriethylammonium chloride After dissolving 4.1 g of PGME682g, it was made to react at 130 degreeC for 24 hours, and the solution (solid content concentration 20 mass%) containing polyurea (L1) was obtained. As a result of GPC analysis, the obtained polyurea (L1) had Mw of 8,000 and Mw/Mn of 1.5.

[Synthesis Example 2] Synthesis of acrylic polymer (S1) 4.02 g of HFiPMA, 2.22 g of HPMA, 4.00 g of ADMA and 0.47 g of AIBN were dissolved in 49.1 g of PGME and reacted at 70° C. for 20 hours to prepare an acrylic polymer (S1) solution. (Solid content concentration 20% by mass) was obtained. The composition ratio of each unit was HFiPMA:HPMA:ADMA=30:30:40. As a result of GPC analysis, the acrylic polymer (S1) obtained had Mw of 5,040 and Mw/Mn of 1.7.

[Synthesis Example 3] Synthesis of acrylic polymer (S2) 3.98 g of HFiPMA, 2.43 g of HPMA, 5.00 g of IBXA and 0.46 g of AIBN were dissolved in 49.8 g of PGME and reacted at 70°C for 20 hours to prepare an acrylic polymer (S2) solution. (Solid content concentration 20% by mass) was obtained. The composition ratio of each unit was HFiPMA:HPMA:IBXA=30:30:40. As a result of GPC analysis, the acrylic polymer (S2) obtained had Mw of 4,720 and Mw/Mn of 1.7.

[2] Preparation of Resin Substrate Forming Composition [Preparation Example 1] Preparation of Resin Substrate Forming Composition F1 In a round-bottomed flask containing 100 g of carbon tetrachloride, ZEONOR (registered trademark) 1020R (manufactured by ZEON CORPORATION) 10 g of olefin polymer and 3 g of Epolide (registered trademark) GT401 (manufactured by Daicel Corporation) were added. This solution was stirred and dissolved in a nitrogen atmosphere for 24 hours to prepare a resin substrate-forming composition F1.

[3] Preparation of Release Layer Forming Composition for Slit Die Coat [Example 1-1] Preparation of Release Layer Forming Composition 1 20 g of the reaction solution obtained in Synthesis Example 1 was mixed with 1.00 g of PL-LI and 0.005 of PPTS. 12 g, an acrylic polymer (S1) solution 1.50 g and PGMEA were added, and diluted with PGME so that the solid content concentration was 5% by mass and the PGMEA concentration was 30% by mass to prepare a release layer forming composition 1.

[Example 1-2] Preparation of release layer-forming composition 2 The release layer was prepared in the same manner as in Example 1-1, except that the solid content concentration was 5% by mass and the PGMEA concentration was 70% by mass. A forming composition 2 was prepared.

[Example 1-3] Preparation of release layer-forming composition 3 Example 1 was repeated except that EL was used instead of PGMEA so that the solid content concentration was 5% by mass and the EL concentration was 30% by mass. A release layer-forming composition 3 was prepared in the same manner as in -1.

[Example 1-4] Preparation of release layer-forming composition 4 Example 1 was repeated except that EL was used instead of PGMEA so that the solid content concentration was 5% by mass and the EL concentration was 70% by mass. A release layer-forming composition 4 was prepared in the same manner as in -1.

[Example 1-5] Preparation of release layer-forming composition 5 Example 1 was repeated except that GBL was used instead of PGMEA so that the solid content concentration was 5% by mass and the GBL concentration was 30% by mass. A release layer forming composition 5 was prepared in the same manner as in -1.

[Example 1-6] Preparation of release layer-forming composition 6 Example 1 was repeated except that GBL was used instead of PGMEA so that the solid content concentration was 5% by mass and the GBL concentration was 10% by mass. A release layer-forming composition 6 was prepared in the same manner as in -1.

[Example 1-7] Preparation of release layer-forming composition 7 Example 1 was repeated except that Triglyme was used instead of PGMEA so that the solid content concentration was 5% by mass and the Triglyme concentration was 30% by mass. A release layer forming composition 7 was prepared in the same manner as in -1.

[Example 1-8] Preparation of release layer-forming composition 8 Example 1 was repeated except that Triglyme was used instead of PGMEA so that the solid content concentration was 5% by mass and the Triglyme concentration was 10% by mass. A release layer forming composition 8 was prepared in the same manner as in -1.

[Example 1-9] Preparation of release layer-forming composition 9 Example 1 was repeated except that Diglyme was used instead of PGMEA so that the solid content concentration was 5 mass% and the Diglyme concentration was 10 mass %. A release layer forming composition 9 was prepared in the same manner as in -1.

[Example 1-10] Preparation of release layer-forming composition 10 Example 1 was repeated except that DEGEEA was used instead of PGMEA so that the solid content concentration was 5% by mass and the DEGEEA concentration was 30% by mass. A release layer forming composition 10 was prepared in the same manner as in -1.

[Example 1-11] Preparation of release layer-forming composition 11 To 20 g of the reaction solution obtained in Synthesis Example 1, PL-LI (1.28 g), PPTS (0.12 g), acrylic polymer (S1) solution (6.00 g) and PGMEA were added. In addition, a release layer-forming composition 11 was prepared by diluting with PGME so that the solid content concentration was 5% by mass and the PGMEA concentration was 30% by mass.

[Example 1-12] Preparation of release layer forming composition 12 To 20 g of the reaction solution obtained in Synthesis Example 1, PL-LI 1.00 g, PPTS 0.12 g, acrylic polymer (S2) solution 1.50 g and PGMEA were added. In addition, the release layer forming composition 12 was prepared by diluting with PGM such that the solid content concentration was 5% by mass and the PGMEA concentration was 30% by mass.

[Example 1-13] Preparation of release layer-forming composition 13 To 20 g of the reaction solution obtained in Synthesis Example 1, PL-LI 1.00 g, PPTS 0.60 g, acrylic polymer (S2) solution 1.50 g and GBL were added. In addition, the release layer-forming composition 13 was prepared by diluting with PGME so that the solid content concentration was 5% by mass and the GBL concentration was 30% by mass.

[Example 1-14] Preparation of release layer-forming composition 14 To 20 g of the reaction solution obtained in Synthesis Example 1, PL-LI (1.00 g), PPTS (0.60 g), acrylic polymer (S1) solution (1.50 g) and PGMEA were added. In addition, the release layer-forming composition 14 was prepared by diluting with PGME so that the solid content concentration was 5% by mass and the PGMEA concentration was 30% by mass.

[Example 1-15] Preparation of release layer-forming composition 15 To 1 g of the reaction solution obtained in Synthesis Example 1, 3,3'-5,5'-tetrakis(methoxymethyl)-[1,1'- Biphenyl]-4,4'-diol 0.06 g, PPTS 0.01 g, acrylic polymer (S1) solution 0.08 g, and PGMEA were added so that the solid content concentration was 5% by mass and the PGMEA concentration was 30% by mass. It was diluted with PGME to prepare a release layer-forming composition 15.

[Comparative Example 1] Preparation of release layer forming composition 16 Example 1-1 except that PGME was used instead of PGMEA so that the solid content concentration was 5% by mass and the PGME concentration was 95% by mass. A release layer-forming composition 16 was prepared in the same manner as in.

[4] Preparation of release layer and evaluation thereof [Example 2-1]
The composition 1 for forming a release layer was formed on a glass substrate (100 mm×100 mm, the same applies hereinafter) with a slit die coater (manufactured by Techno Machine Co., Ltd., product name: table die, conditions: liquid volume 7 μL, gap 25 μm, coating speed 20 mm/ sec) was used for coating. After that, the obtained coating film was made to reach a reduced pressure level in 5 seconds by a vacuum desiccator (a reduced pressure level of 60 Pa) and vacuum dried. Next, using a hot plate, heating at 100° C. for 2 minutes, and further using a hot plate at 230° C. for 10 minutes, a peeling layer having a thickness of about 0.1 μm is formed on the glass substrate. A glass substrate 1 was obtained.

[Example 2-2]
A glass substrate 2 with a release layer was obtained in the same manner as in Example 2-1, except that the release layer forming composition 2 was used in place of the release layer forming composition 1.

[Example 2-3]
A glass substrate 3 with a release layer was obtained in the same manner as in Example 2-1, except that the release layer forming composition 3 was used in place of the release layer forming composition 1.

[Example 2-4]
A glass substrate 4 with a release layer was obtained in the same manner as in Example 2-1, except that the release layer forming composition 4 was used in place of the release layer forming composition 1.

[Example 2-5]
A glass substrate 5 with a release layer was obtained in the same manner as in Example 2-1, except that the release layer forming composition 5 was used in place of the release layer forming composition 1.

[Example 2-6]
A glass substrate 6 with a release layer was obtained in the same manner as in Example 2-1, except that the release layer forming composition 6 was used in place of the release layer forming composition 1.

[Example 2-7]
A glass substrate 7 with a release layer was obtained in the same manner as in Example 2-1, except that the release layer forming composition 7 was used in place of the release layer forming composition 1.

[Example 2-8]
A glass substrate 8 with a release layer was obtained in the same manner as in Example 2-1, except that the release layer forming composition 8 was used in place of the release layer forming composition 1.

[Example 2-9]
A glass substrate 9 with a release layer was obtained in the same manner as in Example 2-1, except that the release layer forming composition 9 was used in place of the release layer forming composition 1.

[Example 2-10]
A glass substrate 10 with a release layer was obtained in the same manner as in Example 2-1, except that the release layer forming composition 10 was used in place of the release layer forming composition 1.

[Example 2-11]
A glass substrate 11 with a release layer was obtained in the same manner as in Example 2-1, except that the release layer forming composition 11 was used in place of the release layer forming composition 1.

[Example 2-12]
A glass substrate 12 with a release layer was obtained in the same manner as in Example 2-1, except that the release layer forming composition 12 was used in place of the release layer forming composition 1.

[Example 2-13]
A glass substrate 13 with a release layer was obtained in the same manner as in Example 2-1, except that the release layer forming composition 13 was used in place of the release layer forming composition 1.

[Example 2-14]
A glass substrate 14 with a release layer was obtained in the same manner as in Example 2-1, except that the release layer-forming composition 14 was used in place of the release layer-forming composition 1.

[Example 2-15]
A glass substrate 15 with a release layer was obtained in the same manner as in Example 2-1, except that the release layer forming composition 15 was used in place of the release layer forming composition 1.

[Comparative Example 2-1]
A glass substrate 16 with a release layer was obtained in the same manner as in Example 2-1, except that the release layer forming composition 16 was used in place of the release layer forming composition 1. When the unevenness of the peeling layer was confirmed with a Na lamp, the peeling layer became cloudy and many irregularities were confirmed.

[5] Production of Resin Substrate [Example 3-1]
The composition F1 for resin substrate formation was applied onto the release layer (resin thin film) on the glass substrate by using a spin coater (condition: rotation speed 200 rpm for about 15 seconds) on the glass substrate 1 with release layer. The obtained coating film is heated at 80° C. for 2 minutes using a hot plate, and then 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 resin substrate/glass substrate 1 with a release layer was obtained. Then, the light transmittance was measured using an ultraviolet-visible spectrophotometer (UV-2600 manufactured by Shimadzu Corporation), and as a result, the resin substrate showed a transmittance of 90% or more at 400 nm.

[Example 3-2]
A resin substrate/release layer-attached glass substrate 2 was obtained in the same manner as in Example 3-1, except that the release layer-attached glass substrate 2 was used instead of the release layer-attached glass substrate 1. The resin substrate showed a transmittance of 90% or more at 400 nm.

[Example 3-3]
A resin substrate/glass substrate with release layer 3 was obtained in the same manner as in Example 3-1, except that the glass substrate with release layer 3 was used instead of the glass substrate with release layer 1. The resin substrate showed a transmittance of 90% or more at 400 nm.

[Example 3-4]
A resin substrate/release layer-attached glass substrate 4 was obtained in the same manner as in Example 3-1, except that the release layer-attached glass substrate 4 was used instead of the release layer-attached glass substrate 1. The resin substrate showed a transmittance of 90% or more at 400 nm.

[Example 3-5]
A resin substrate/glass substrate with release layer 5 was obtained in the same manner as in Example 3-1, except that the glass substrate with release layer 5 was used instead of the glass substrate with release layer 1. The resin substrate showed a transmittance of 90% or more at 400 nm.

[Example 3-6]
A resin substrate/glass substrate with release layer 6 was obtained in the same manner as in Example 3-1, except that the glass substrate with release layer 6 was used instead of the glass substrate with release layer 1. The resin substrate showed a transmittance of 90% or more at 400 nm.

[Example 3-7]
A resin substrate/glass substrate with release layer 7 was obtained in the same manner as in Example 3-1, except that the glass substrate with release layer 7 was used instead of the glass substrate with release layer 1. The resin substrate showed a transmittance of 90% or more at 400 nm.

[Example 3-8]
A resin substrate/glass substrate with release layer 8 was obtained in the same manner as in Example 3-1, except that the glass substrate with release layer 8 was used instead of the glass substrate with release layer 1. The resin substrate showed a transmittance of 90% or more at 400 nm.

[Example 3-9]
A resin substrate/release layer-attached glass substrate 9 was obtained in the same manner as in Example 3-1, except that the release layer-attached glass substrate 9 was used instead of the release layer-attached glass substrate 1. The resin substrate showed a transmittance of 90% or more at 400 nm.

[Example 3-10]
A resin substrate/release layer-attached glass substrate 10 was obtained in the same manner as in Example 3-1, except that the release layer-attached glass substrate 10 was used instead of the release layer-attached glass substrate 1. The resin substrate showed a transmittance of 90% or more at 400 nm.

[Example 3-11]
A resin substrate/glass substrate with release layer 11 was obtained in the same manner as in Example 3-1, except that the glass substrate with release layer 11 was used instead of the glass substrate with release layer 1. The resin substrate showed a transmittance of 90% or more at 400 nm.

[Example 3-12]
A resin substrate/glass substrate with release layer 12 was obtained in the same manner as in Example 3-1, except that the glass substrate with release layer 12 was used instead of the glass substrate with release layer 1. The resin substrate showed a transmittance of 90% or more at 400 nm.

[Example 3-13]
A resin substrate/release layer-attached glass substrate 13 was obtained in the same manner as in Example 3-1, except that the release layer-attached glass substrate 13 was used in place of the release layer-attached glass substrate 1. The resin substrate showed a transmittance of 90% or more at 400 nm.

[Example 3-14]
A resin substrate/release layer-attached glass substrate 14 was obtained in the same manner as in Example 3-1, except that the release layer-attached glass substrate 14 was used in place of the release layer-attached glass substrate 1. The resin substrate showed a transmittance of 90% or more at 400 nm.

[Example 3-15]
A resin substrate/release layer-attached glass substrate 15 was obtained in the same manner as in Example 3-1 except that the release layer-attached glass substrate 15 was used in place of the release layer-attached glass substrate 1. The resin substrate showed a transmittance of 90% or more at 400 nm.

[6] Evaluation of Releasability With respect to the glass substrates 1 to 16 with release layer, the adhesion between the release layer and the glass substrate was evaluated with respect to the resin substrate and the glass substrates with release layer 1 to 15 without release layer unevenness. The peelability from the resin film was confirmed by the following method. The following tests were conducted on the same glass substrate.

(1) Evaluation of Adhesion between Release Layer and Glass Substrate The release layers on the glass substrates 1 to 16 with release layer were cross-cut (2 mm in length and width, the same applies hereinafter), and 25 mass cuts were performed. That is, this cross cut formed 25 squares of 2 mm square. An adhesive tape was attached to the 25 muscat portion, the tape was peeled off, and the adhesiveness was evaluated based on the following criteria. The results are shown in Table 1.
<Judgment criteria>
5B: 0% peeling (no peeling)
4B: less than 5% peeling 3B: 5 to less than 15% peeling 2B: 15 to less than 35% peeling 1B: 35 to less than 65% peeling 0B: 65% to less than 80% peeling B: 80% to 95% % Peeling A: 95% to less than 100% peeling AA: 100% peeling (all peeling)

(2) Evaluation of Peeling Force between Release Layer and Resin Substrate Strips of 25 mm×50 mm were prepared on the glass substrates 1 to 15 with resin substrate/release layer. Furthermore, after sticking Cellotape (registered trademark) (CT-24 manufactured by Nichiban Co., Ltd.), using an autograph AGS-X500N (manufactured by Shimadzu Corporation) at a peeling angle of 90° and a peeling speed of 300 mm/min. It peeled and the peeling force was measured. Those that could not be peeled were not peeled. The results are shown in Table 1.

From the results shown in Table 1, the peeling layer of the example was excellent in adhesion to the glass substrate and also excellent in peeling from the resin substrate. On the other hand, the peeling layer of Comparative Example had many irregularities on the surface and was cloudy.

From the above results, by using the composition for forming a release layer for slit die coating of the present invention, even when applied by the slit die coating method, coating unevenness does not occur, excellent adhesion with the substrate, moderate with the resin substrate It was shown that a peeling layer having good adhesion and moderate peelability can be obtained.

Claims

(A) a polyurea containing a repeating unit represented by the following formula (1),
(B) an acid compound or a salt thereof,
(C) a cross-linking agent selected from compounds having a nitrogen atom substituted with a hydroxyalkyl group and/or an alkoxymethyl group,
(D) A polymer additive containing a repeating unit represented by the following formula (a1), a repeating unit represented by the following formula (b) and a repeating unit represented by the following formula (c), and (E) 20 Including a solvent containing at least one solvent having a vapor pressure at 800° C. of 800 Pa or less,
A composition for forming a release layer for a slit die coat, wherein the polymer additive (D) is contained in an amount of 3 to 100 parts by mass relative to 100 parts by mass of the polyurea (A).

[In the formula, A 1 , A 2 , A 3 , A 4 , A 5 and A 6 are each independently a hydrogen atom, a methyl group or an ethyl group,
X 1 is a group represented by the following formula (1-1), (1-2), (1-3) or (1-4),

(In the formula, R 1 and R 2 are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 3 to 6 carbon atoms, a benzyl group or a phenyl group, and the phenyl group is a carbon atom. Substituted with at least one group selected from the group consisting of an alkyl group having 1 to 6 carbon atoms, a halogen atom, an alkoxy group having 1 to 6 carbon atoms, a nitro group, a cyano group, a hydroxy group and an alkylthio group having 1 to 6 carbon atoms. R 1 and R 2 may combine with each other to form a ring having 3 to 6 carbon atoms together with the carbon atom to which they are bonded, and R 3 has 1 to 6 carbon atoms. An alkyl group, an alkenyl group having 3 to 6 carbon atoms, a benzyl group or a phenyl group, wherein the phenyl group is an alkyl group having 1 to 6 carbon atoms, a halogen atom, an alkoxy group having 1 to 6 carbon atoms, a nitro group, cyano May be substituted with at least one group selected from the group consisting of a group, a hydroxy group and an alkylthio group having 1 to 6 carbon atoms.)
Q 1 is a group represented by the following formula (1-5) or (1-6).

(In the formula, X 2 is a group represented by the formula (1-1), the formula (1-2) or the formula (1-4), and Q 2 is an alkylene group having 1 to 10 carbon atoms, or phenylene. Group, naphthylene group or anthrylene group, wherein the phenylene group, naphthylene group and anthrylene group are an alkyl group having 1 to 6 carbon atoms, a halogen atom, an alkoxy group having 1 to 6 carbon atoms, a nitro group, a cyano group, a hydroxy group. , And at least one group selected from the group consisting of alkylthio groups having 1 to 6 carbon atoms, and n 1 and n 2 are each independently 0 or 1.)]

(In the formula, R A is each independently a hydrogen atom or a methyl group, and R B1 is a branched alkyl group having 3 or 4 carbon atoms in which at least one hydrogen atom is substituted with a fluorine atom, R C is a hydroxyalkyl group having 1 to 10 carbon atoms, and R D is a polycyclic alkyl group having 6 to 20 carbon atoms or an aryl group having 6 to 12 carbon atoms.)
(D) In the repeating unit represented by the formula (b) of the polymer additive, R C is a hydroxyalkyl group having 2 to 10 carbon atoms, and the carbon atom to which the hydroxy group is bonded is a secondary carbon atom. And the content ratio of the repeating unit represented by the formula (a1) is 30 mol% or more based on all repeating units of the polymer additive (D), for forming a release layer for a slit die coat. Composition.
The composition for forming a release layer for slit die coating according to claim 1 or 2, wherein X 1 is a group represented by the formula (1-3).
The composition for forming a release layer for slit die coating according to claim 3 , wherein R 3 is a 2-propenyl group.
Q 1 is a group represented by the formula (1-5), wherein the composition for forming a release layer for slit die coat according to any one of claims 1 to 4.
The composition for forming a release layer for a slit die coat according to any one of claims 1 to 5, wherein the component (B) is a sulfonic acid compound or a salt thereof.
The composition for forming a release layer for a slit die coat according to any one of claims 1 to 6, wherein the crosslinking agent (C) is a compound represented by any one of the following formulas (C-1) to (C-7). Stuff.

(In the formula, R 11 to R 38 are each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and R 39 is a hydrogen atom or a methyl group.)
The composition for forming a release layer for a slit die coat according to any one of claims 1 to 7, wherein the content of (C) the cross-linking agent is 10 to 100 parts by mass relative to 100 parts by mass of (A) polyurea.
A release layer obtained from the composition for forming a release layer for slit die coating according to any one of claims 1 to 8.
A laminate in which the release layer according to claim 9 is laminated with a resin layer having a light transmittance of 80% or more at a wavelength of 400 nm.
A step of applying a release layer-forming composition for slit die coat according to any one of claims 1 to 8 to a substrate to form a release layer,
Manufacture of a resin substrate including a step of forming a resin substrate having a light transmittance of 400 nm at a wavelength of 80% or more on the peeling layer, and a step of peeling the resin substrate with a peeling force of 0.15 N/25 mm or less Method.