TW202140698A - Composition for forming release layer for alkali glass, and release layer - Google Patents

Abstract

A composition for forming a release layer for alkali glass, said composition containing the components (A) to (E) described below. If a film, which is obtained by applying this composition onto an alkali glass substrate and subsequently firing this composition at 300 DEG C or less, is brought into contact with an organic film, the film has a release strength of 0.2 N/25 mm or less. (A) a polyurea which contains a repeating unit represented by formula (1) (B) a sulfonic acid compound or a salt thereof (C) a crosslinking agent which is selected from among compounds having a nitrogen atom that is 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 which is in an amount of from 3 to 100 parts by mass relative to 100 parts by mass of the polyurea (A) (E) a solvent (In the formulae, each RA independently represents a hydrogen atom or a methyl group; RB1 represents a branched alkyl group having 3 or 4 carbon atoms, wherein at least one hydrogen atom is substituted by a fluorine atom; RC represents a hydroxyalkyl group having from 1 to 10 carbon atoms; and RD represents a polycyclic alkyl group having from 6 to 20 carbon atoms or an aryl group having from 6 to 12 carbon atoms.).

Description

Composition for forming peeling layer for alkali glass and peeling layer

The present invention relates to a composition for forming a peeling layer for alkali glass and a peeling layer.

In recent years, in addition to the characteristics of thinning and lightening of electronic devices, it is also necessary to provide functions such as being able to bend. From this point of view, it is required to use a lightweight flexible plastic substrate instead of the conventional heavy, fragile, and inflexible glass substrate.

In particular, in the new generation of displays, the development of active matrix full-color TFT display panels using a lightweight flexible plastic substrate (hereinafter, also referred to as a resin substrate) is required. In addition, in the touch panel display, materials corresponding to flexibility such as transparent electrodes and resin substrates of the touch panel used in the display panel are being developed. As transparent electrodes, other transparent electrode materials such as transparent conductive polymers such as PEDOT that can be bent, metal nanowires, and their hybrid systems have been proposed from ITO used in the past (Patent Documents 1 to 4). As a technique for fabricating the flexible touch sensor wiring, for example, a wiring technique by flexographic printing using a metal nanowire and a high-boiling solvent (Patent Document 5), however, is different from the past In addition to being very easy to bend, on the other hand, due to the use of high-boiling solvents, ITO requires high-temperature processes that were not required in the past.

On the other hand, the substrate of the touch panel film also uses glass to sheets made of plastics such as polyethylene terephthalate (PET), polyimide, cycloolefin, acrylic, etc., to develop It is necessary to maintain a flexible transparent flexible touch screen panel and a substrate that can withstand high-temperature processes (Patent Documents 6 to 8).

Generally speaking, in order to achieve stable productivity and releasability, a peeling (adhesive) layer is made on a supporting substrate such as a glass substrate, and a device is made on it and then peeled off to produce a flexible touch screen panel (Patent Document 9). At this time, from the viewpoint of the manufacturing process, the touch screen panel is cut according to each glass substrate, and the touch screen panel is cut into small pieces and peeled off. Therefore, the glass substrate used cannot be reused, so there is a demand for cheap glass such as alkali glass. In addition, the used peeling layer cannot be peeled from the supporting substrate during the step, but on the other hand, low peeling force is required for peeling. [Prior Technical Literature] [Patent Literature]

[Patent Document 1] International Publication No. 2012/147235 [Patent Document 2] JP 2009-283410 A [Patent Document 3] Japanese Special Publication No. 2010-507199 [Patent Document 4] JP 2009-205924 A [Patent Document 5] Japanese Patent Application Publication No. 2015-166145 [Patent Document 6] International Publication No. 2017/002664 [Patent Document 7] International Publication No. 2016/160338 [Patent Document 8] Japanese Patent Application Publication No. 2015-166145 [Patent Document 9] JP 2016-531358 A

[The problem to be solved by the invention]

The present invention was made in view of the foregoing circumstances, and its purpose is to provide a peeling layer that has high heat resistance and moderate peelability, and even if a cheap alkali glass substrate is used, a peeling layer with excellent peelability and stability can be obtained Forming composition. [Means used to solve the problem]

The inventors of the present invention have repeatedly conducted active reviews in order to achieve the foregoing objective and found a polyurea containing (A) a specific repeating unit, (B) an acid compound or its salt, and (C) a hydroxyalkyl group and / Or a crosslinking agent selected from compounds with nitrogen atoms substituted by alkoxymethyl, (D) polymer additives containing specific repeating units, and (E) a composition for forming a release layer of a solvent, which is reproducible A release layer with high heat resistance, excellent adhesion to the substrate, moderate adhesion to the resin substrate, and moderate releasability is provided, and the present invention is completed.

[式中，A¹ 、A² 、A³ 、A⁴ 、A⁵ 及A⁶ 係各自獨立為氫原子、甲基或乙基， X¹ 為下述式(1-1)、(1-2)、(1-3)或(1-4)所表示之基，

(式中，R¹ 及R² 係各自獨立為氫原子、碳數1~6之烷基、碳數3~6之烯基、苄基或苯基，前述苯基亦可被由碳數1~6之烷基、鹵素原子、碳數1~6之烷氧基、硝基、氰基、羥基及碳數1~6之烷硫基所成之群所選出之至少1種基取代，又，R¹ 及R² 亦可互相鍵結，並與此等所鍵結之碳原子共同形成碳數3~6之環，R³ 為碳數1~6之烷基、碳數3~6之烯基、苄基或苯基，前述苯基亦可被由碳數1~6之烷基、鹵素原子、碳數1~6之烷氧基、硝基、氰基、羥基及碳數1~6之烷硫基所成之群所選出之至少1種基取代。) Q¹ 為下述式(1-5)或(1-6)所表示之基。

(式中，X² 為式(1-1)、式(1-2)或式(1-4)所表示之基，Q² 為碳數1~10之伸烷基、伸苯基、伸萘基或伸蒽基，前述伸苯基、伸萘基及伸蒽基亦可被由碳數1~6之烷基、鹵素原子、碳數1~6之烷氧基、硝基、氰基、羥基，及碳數1~6之烷硫基所成之群所選出之至少1種基取代，n¹ 及n² 係各自獨立為0或1。)]

(式中，R^A 係各自獨立為氫原子或甲基，R^B1 係至少1個氫原子被氟原子取代之碳數3或4之分支狀之烷基，R^C 係具有碳數2~10之羥烷基或1~4個之羥基之碳數之6~20之多環式烷基，R^D 為碳數6~20之多環式烷基或碳數6~12之芳基。) 2. 如1之鹼玻璃用剝離層形成用組成物，其中，(D)高分子添加劑之式(b)所表示之重複單元中，R^C 為具有碳數2~10之羥烷基或1~4個之羥基之碳數6~20之多環式烷基，其中，羥基所鍵結之碳原子為第2級或第3級碳原子，且，式(a1)所表示之重複單元之含有比例係在(D)高分子添加劑之全重複單元中為20莫耳%以上80莫耳%以下。 3. 如1或2之鹼玻璃用剝離層形成用組成物，其中，X¹ 為式(1-3)所表示之基。 4. 如3之鹼玻璃用剝離層形成用組成物，其中，R³ 為2-丙烯基。 5. 如1~4中之任一者之鹼玻璃用剝離層形成用組成物，其中，Q¹ 為式(1-5)所表示之基。 6. 如1~6中之任一者之鹼玻璃用剝離層形成用組成物，其中，(C)交聯劑係下述式(C-1)~(C-7)中之任一者所表示之化合物。

(式中，R¹¹ ~R³⁸ 係各自獨立為氫原子或碳數1~5之烷基，R³⁹ 為氫原子或甲基。) 7. 如1~6中之任一者之鹼玻璃用剝離層形成用組成物，其中，(C)交聯劑之含量相對於(A)聚脲100質量份，為10~100質量份。 8. 一種剝離層，其係由1~7中之任一者之鹼玻璃用剝離層形成用組成物所獲得。 9. 一種積層體，其係於8之剝離層上積層有波長400nm之光透過率為80%以上之樹脂層。 10. 一種樹脂基板之製造方法，其係包含： 將如1~7中之任一者之鹼玻璃用剝離層形成用組成物塗布於基體上，形成剝離層之步驟、 於前述剝離層上形成波長400nm之光透過率為80%以上之樹脂基板之步驟，及 將前述樹脂基板以0.2N/25mm以下之剝離力進行剝離之步驟。 [發明效果]That is, the present invention provides the following composition for forming a peeling layer for alkali glass and a peeling layer. 1. A composition for forming a peeling layer for alkali glass, which contains the following components (A) to (E) and is coated on an alkali glass substrate and then sintered at a temperature of 300°C or less. It is in contact with an organic thin film In this case, it has a peeling force of 0.2N/25mm or less. (A) Polyurea containing a repeating unit represented by the following formula (1), (B) a sulfonic acid compound or its salt, (C) a nitrogen atom substituted by a hydroxyalkyl group and/or an alkoxymethyl group The crosslinking agent selected by the compound, (D) contains the repeating unit represented by the following formula (a1), the repeating unit represented by the following formula (b), and the repeating unit represented by the following formula (c). Molecular additives: 3-100 parts by mass relative to 100 parts by mass of (A) polyurea, (E) solvent

[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, and X ¹ is 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 with 1 to 6 carbons, an alkenyl group with 3 to 6 carbons, a benzyl group, or a phenyl group. ~6 alkyl group, halogen atom, C1-C6 alkoxy group, nitro group, cyano group, hydroxyl group and C1-C6 alkylthio group selected by at least one group substituted, and , R ¹ and R ² can also be bonded to each other, and together with these bonded carbon atoms form a ring with carbon number of 3-6, R ³ is an alkyl group with carbon number of 1 to 6, and a carbon number of 3-6 Alkenyl, benzyl, or phenyl. The aforementioned phenyl group can also be composed of an alkyl group with 1 to 6 carbons, a halogen atom, an alkoxy group with 1 to 6 carbons, a nitro group, a cyano group, a hydroxyl group, and a carbon number of 1~ At least one group selected from the group of 6 alkylthio groups is substituted.) 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 formula (1-1), formula (1-2) or formula (1-4), and Q ² is an alkylene group, phenylene group, and a Naphthyl or anthrylene, the aforementioned phenyl, naphthyl, and anthracenyl groups can also be composed of alkyl groups with 1 to 6 carbon atoms, halogen atoms, alkoxy groups with 1 to 6 carbon atoms, nitro groups, and cyano groups. , Hydroxyl, and at least one group selected from the group of alkylthio groups with 1 to 6 carbon atoms, 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, R ^B1 is a branched alkyl group with 3 or 4 carbon atoms in which at least one hydrogen atom is replaced by a fluorine atom, and R ^C has a carbon number of 2-10 The hydroxyalkyl group or the polycyclic alkyl group of 6-20 carbons with 1 to 4 hydroxy groups, R ^D is a polycyclic alkyl group with 6-20 carbons or an aryl group with 6-12 carbons.) 2. The composition for forming a peeling layer for alkali glass as in 1, wherein, in the repeating unit represented by formula (b) of (D) polymer additive, R ^C is a hydroxyalkyl group having 2 to 10 carbon atoms or 1 ~4 hydroxy groups and a polycyclic alkyl group with 6 to 20 carbon atoms, wherein the carbon atom to which the hydroxy group is bonded is the second or third level carbon atom, and the repeating unit represented by the formula (a1) The content ratio is 20 mol% or more and 80 mol% or less in the total repeating unit of the (D) polymer additive. 3. The composition for forming a peeling layer for alkali glass as described in 1 or 2, wherein X ¹ is a group represented by formula (1-3). 4. The composition for forming a peeling layer for alkali glass according to 3, wherein R ³ is a 2-propenyl group. 5. The composition for forming a peeling layer for alkali glass according to any one of 1 to 4, wherein Q ¹ is a group represented by formula (1-5). 6. The composition for forming a peeling layer for alkali glass according to any one of 1 to 6, wherein the (C) crosslinking agent is any one of the following formulas (C-1) to (C-7) The compound represented.

(In the formula, R ¹¹ to R ³⁸ are each independently a hydrogen atom or an alkyl group with 1 to 5 carbon atoms, and R ³⁹ is a hydrogen atom or a methyl group.) 7. Such as any one of 1 to 6 for alkali glass In the composition for forming a release layer, the content of the (C) crosslinking agent is 10 to 100 parts by mass with respect to 100 parts by mass of the (A) polyurea. 8. A peeling layer obtained from the composition for forming a peeling layer for alkali glass of any one of 1 to 7. 9. A laminated body, which is laminated with a resin layer with a wavelength of 400nm and a light transmittance of 80% or more on the release layer of 8. 10. A method of manufacturing a resin substrate, which comprises: coating the composition for forming a peeling layer for alkali glass as in any one of 1 to 7 on a substrate to form a peeling layer, and forming on the peeling layer A step of a resin substrate with a light transmittance of 80% or more at a wavelength of 400nm, and a step of peeling the aforementioned resin substrate with a peeling force of 0.2N/25mm or less. [Effects of the invention]

By using the composition for forming a peeling layer of the present invention, peeling with high heat resistance, excellent adhesion to the substrate, moderate adhesion to the resin substrate, and moderate releasability can be obtained with good reproducibility Floor. In addition, in the manufacturing process of the flexible electronic device, the resin substrate formed on the substrate, or the circuit further provided on the substrate, can be separated from the substrate at the same time without causing damage to the circuit or the like. Therefore, the composition for forming a release layer of the present invention contributes to the speeding up of the manufacturing process of flexible electronic devices provided with resin substrates and the improvement of yield.

[Composition for forming peeling layer]

The composition for forming a release layer of the present invention includes (A) a polyurea containing a specific repeating unit, (B) an acid compound or a salt thereof, and (C) a compound substituted with a hydroxyalkyl group and/or an alkoxymethyl group A crosslinking agent selected from a compound having a nitrogen atom, (D) a polymer additive containing a specific repeating unit, and (E) a solvent.

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

In 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. From the standpoint of releasability and productivity, A ¹ ~ Preferably, all A ⁶ are 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 with 1 to 6 carbons, an alkenyl group with 3 to 6 carbons, a benzyl group or a phenyl group, The aforementioned phenyl group can also be a group consisting of alkyl groups with carbon numbers 1 to 6, halogen atoms, alkoxy groups with carbon numbers 1 to 6, nitro, cyano, hydroxyl, and alkylthio groups with carbon numbers 1 to 6 At least one selected group is substituted, and R ¹ and R ² can also be bonded to each other, and together with these bonded carbon atoms form a ring with 3-6 carbon atoms.

In the formula (1-3), R ³ is an alkyl group with 1 to 6 carbons, an alkenyl group with 3 to 6 carbons, a benzyl group or a phenyl group. The aforementioned phenyl group may also be substituted with an alkyl group with 1 to 6 carbons , Halogen atom, C1-C6 alkoxy group, nitro group, cyano group, hydroxyl group and C1-C6 alkylthio group selected at least one group substituted. )

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, in the case where X ² is the group represented by the formula (1-2), its structure is the formula (1-5-1).

(式中，R¹ 及R² 係與前述相同。)

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

In the formula (1-6), Q ² is an alkylene group, phenylene group, naphthylene group or anthrylene group having 1 to 10 carbon atoms. The aforementioned phenylene, naphthyl and anthracene groups can also be formed by alkyl groups with 1 to 6 carbon atoms, halogen atoms, alkoxy groups with 1 to 6 carbon atoms, nitro groups, cyano groups, hydroxyl groups, and carbon numbers 1. At least one group selected from the group of ~6 alkylthio groups is substituted. In addition, when Q ² is a phenylene group, a naphthylene group, or an anthracene group, the bonding position of these groups is not particularly limited. That is, for example, when the phenylene group is bonded at the 1-position and the 2-position, the 1-position and the 3-position are bonded, or the 1-position and the 4-position are bonded, the naphthylene is bonded at the 1-position. When bonding with two positions, when bonding with one and four positions, when bonding with one and five positions, or when bonding with two and three positions, the anthracene group is 1 It is possible to bond with two bits and two bits, bond with one and four bits, or bond with nine and ten bits, but any of them may be used.

The alkyl group having 1 to 6 carbon atoms may be any of linear, branched, and cyclic. Examples include methyl, ethyl, isopropyl, n-butyl, and cyclohexyl. Wait. The alkenyl group having 3 to 6 carbon atoms may be any one of linear, branched, and cyclic. Examples include 2-propenyl and 3-butenyl.

The alkoxy group having 1 to 6 carbon atoms may be any of linear, branched, and cyclic. Examples include methoxy, ethoxy, isopropoxy, and n-pentyl. Oxy and cyclohexyloxy and so on. The alkylthio group having 1 to 6 carbon atoms may be linear, branched, or cyclic, for example, methylthio, ethylthio, isopropylthio, n-pentylthio Group, cyclohexylthio and so on. As said halogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. are mentioned. In addition, examples of the ring having 3 to 6 carbon atoms formed by the bonding of ^{R 1} and R ^{2 include a cyclobutane ring, a cyclopentane ring, and a cyclohexane ring.}

As the aforementioned C1-10 alkylene group, it may be any of linear, branched, and cyclic. Examples include methylene, ethylene, propylene, and pentamethylene. , Cyclohexyl, 2-Methylpropylene, etc.

In addition, in the formula (1), when X ¹ is the base represented by the formula (1-2), its structure is represented by the following formula (2), and X ¹ is represented by the formula (1-3) In the case of the base, its structure is represented by the following formula (3). In the formula (3), R ³ is preferably a 2-propenyl group.

(式中，A¹ ~A⁶ 、R¹ ~R³ 及Q¹ 係與前述相同。)

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

From the viewpoint of the heat resistance of the polyurea of the component (A), in the formula (1), Q ¹ preferably includes a cyclic structure. That is, Q ¹ is a group represented by formula (1-5) or a group represented by formula (1-6), and Q ² is a cyclic alkylene group, phenylene group, naphthylene group or anthracenyl group Preferably, it is more preferably a group represented by formula (1-5).

The repeating unit represented by formula (1) is preferably represented by the following formula (4) to formula (22). In addition, in the following formula, Me is a methyl group, and Et is an ethyl group.

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

(A) The weight average molecular weight (Mw) of the polyurea is preferably 1,000 to 200,000, more preferably 3,000 to 100,000, still more preferably 4,000 to 30,000, and still more preferably 5,000 to 20,000. In addition, the degree of dispersion (Mw/Mn) 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 measured values in terms of polystyrene obtained by gel permeation chromatography (GPC).

[(B) Acid compound or its salt] The composition for forming a release layer of the present invention contains an acid compound or a salt thereof as the (B) component. Examples of the aforementioned acid compounds include p-toluenesulfonic acid, trifluoromethanesulfonic acid, camphorsulfonic acid, sulfosalic acid, 4-chlorobenzenesulfonic acid, 4-hydroxybenzenesulfonic acid, benzenedisulfonic acid, 1-naphthalene Sulfonic acid compounds such as sulfonic acid. In addition, examples of the salt of the aforementioned acid compound include the aforementioned acid pyridinium salt, isopropanolamine salt, N-methylmorpholine salt, etc., specifically, p-pyridinium toluenesulfonate, 1 -Pyridium naphthalenesulfonate, isopropanolamine p-toluenesulfonate, N-methylmorpholine p-toluenesulfonate, etc.

The content of the component (B) is preferably 1 to 30 parts by mass, and more preferably 10 to 20 parts by mass relative to 100 parts by mass of the polyurea of the component (A). If the content of the component (B) is within the aforementioned range, a composition can be obtained that can provide a peeling layer with high heat resistance and moderate peelability and excellent stability after film formation. (B) An acid compound or its salt system may be used individually by 1 type, and may be used in combination of 2 or more types.

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

The crosslinking agent is preferably a compound represented by any one of the following formulas (C-1) to (C-5).

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

As the aforementioned crosslinking agent, specifically, hexamethylol melamine, tetramethylol benzoguanamine, 1,3,4,6-tetramethylol glycoluril, hexamethoxymethyl melamine, Tetramethoxymethyl benzoguanamine, 1,3,4,6-tetra(methoxymethyl) glycoluril, 1,3,4,6-tetra(butoxymethyl) glycoluril, 1 ,3,4,6-Tetra (hydroxymethyl) glycoluril and other nitrogen-containing compounds.

Also, methoxymethyl melamine compounds (trade names CYMEL (registered trademark) 300, CYMEL 301, CYMEL 303, CYMEL 350) manufactured by ALLNEX Corporation, butoxymethyl melamine compounds (trade name MYCOTE (registered trademark) Trademark) 506, MYCOTE 508), glycoluril compound (trade name CYMEL 1170, POWDERLINK 1174), methylated urea resin (trade name UFR65), butylated urea resin (trade name UFR300, U-VAN10S60, U-VAN10R, U-VAN11HV), DIC (Stock) urea/formaldehyde resin (trade name BECKAMINE (registered trademark) J-300S, BECKAMINEP-955, BECKAMINEN) and other commercially available nitrogen-containing compounds.

In addition, as a crosslinking agent, N-methylol (meth)acrylate, N-methoxymethyl (meth)acrylate, N-ethoxymethyl (meth)acrylic acid can be used. A polymer made of amide, N-butoxymethyl (meth)acrylate and other (meth)acrylate compounds substituted with methylol or alkoxymethyl. Examples of such polymers include poly(N-butoxymethyl(meth)acrylate), copolymers of N-butoxymethyl(meth)acrylate and styrene, Copolymer of N-methylol(meth)acrylamide and meth(meth)acrylate, copolymer of N-ethoxymethacrylamide and benzyl methacrylate, N-butoxy Copolymers of methyl (meth)acrylamide, benzyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate, etc.

As the aforementioned crosslinking agent, more preferable examples include hexamethoxymethyl melamine, tetramethoxymethyl benzoguanamine, 1,3,4,6-tetra(methoxymethyl) glycoluril (POWDERLINK 1174 ), 1,3,4,6-tetra(butoxymethyl) glycoluril, 1,3,4,6-tetra(hydroxymethyl) glycoluril.

These cross-linking agents can cause cross-linking reactions through self-condensation. In addition, it can cause a crosslinking reaction with the hydroxyl group in the polyurea of the component (A). Then, by such a cross-linking reaction, the formed release layer becomes stronger and becomes a release layer with low solubility in organic solvents.

The content of the component (C) is preferably 10-100 parts by mass, more preferably 20-50 parts by mass relative to 100 parts by mass of the polyurea of the component (A). If the content of the component (C) is within the aforementioned range, a composition can be obtained that can provide a peeling layer with high heat resistance and moderate peelability and excellent stability after film formation. (C) The crosslinking agent system may be used individually by 1 type, and may be used in combination of 2 or more types.

[(D) Polymer additives] The composition for forming a release layer of the present invention contains a polymer additive as component (D), and the polymer additive contains a repeating unit represented by the following formula (a1), a repeating unit represented by the following formula (b), and The repeating unit represented by the following formula (c).

In the formula, R ^A is independently-based hydrogen atom or a methyl group. R ^B1 is a branched alkyl group with 3 or 4 carbon atoms in which at least one hydrogen atom is replaced by a fluorine atom. R ^C is a hydroxyalkyl group with 2 to 10 carbons or a polycyclic alkyl group with 6 to 20 carbons and 1 to 4 hydroxyl groups. R ^D is a polycyclic alkyl group with 6 to 20 carbons or an aryl group with 6 to 12 carbons.

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 in these branched alkyl groups is substituted by a fluorine atom. Specific examples include 1,1,1-trifluoroisopropyl, 1,1, 1,3,3,3-hexafluoroisopropyl, nonafluoro tert-butyl, etc.

Examples of the hydroxyalkyl group having 1 to 10 carbon atoms include hydroxymethyl, 2-hydroxyethyl, 3-hydroxypropyl, 4-hydroxybutyl, 5-hydroxypentyl, 6-hydroxyhexyl, and 7-hydroxyethyl. Hydroxyheptyl, 8-hydroxyoctyl, 9-hydroxynonyl, 10-hydroxydecyl, 2-hydroxy-1-methylethyl, 2-hydroxy-1,1-dimethylethyl, 3-hydroxy -1-methylpropyl, 3-hydroxy-2-methylpropyl, 3-hydroxy-1,1-dimethylpropyl, 3-hydroxy-1,2-dimethylpropyl, 3-hydroxyl -2,2-Dimethylpropyl, 4-hydroxy-1-methylbutyl, 4-hydroxy-2-methylbutyl, 4-hydroxy-3-methylbutyl, etc. with carbon number 2~10 The hydroxyalkyl group, and the carbon atom to which the hydroxyl group is bonded is the first level carbon atom; 1-hydroxyethyl, 1-hydroxypropyl, 2-hydroxypropyl, 1-hydroxybutyl, 2-hydroxybutyl Base, 1-hydroxyhexyl, 2-hydroxyhexyl, 1-hydroxyoctyl, 2-hydroxyoctyl, 1-hydroxydecyl, 2-hydroxydecyl, 1-hydroxy-1-methylethyl, 2-hydroxy -2-methylpropyl and other hydroxyalkyl groups with carbon number of 1-10, and the carbon atom to which the hydroxyl group is bonded is the second or third level carbon atom.

As the repeating unit represented by the polycyclic alkyl group having 1 to 4 hydroxyl groups with 6 to 20 carbon atoms, those represented by the following formulas (b-1) to (b-27) can be cited, but they are not Limited to this. In addition, the following formulas, R ^A and the same line.

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

In addition, the (D) polymer additive may include 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 the following The repeating unit represented by formula (d).

In the formula, R ^A , R ^C and R ^D are the same as described above. R ^B2 is a branched alkyl group with 3 or 4 carbon atoms in which at least one hydrogen atom is replaced by a fluorine atom (but, 2-methyl-1,1,1,3,3,3-hexafluoroisopropyl except.). As the aforementioned branched alkyl group having 3 or 4 carbon atoms, the same ones as mentioned above can be mentioned. ^RE is a single bond, a polycyclic alkylene group with 6 to 20 carbons or an aryl alkylene group with 6 to 12 carbons. R ^F is a single bond or an alkylene group with 1 to 10 carbon atoms. R ^G is methyl, ethyl or hydroxyl.

Examples of the aforementioned polycyclic alkylene group having 6 to 20 carbon atoms include a group obtained by removing one hydrogen atom from the specific example of the aforementioned polycyclic alkylene group having 6 to 20 carbon atoms. For example, Adamantyl, isobornyl, subnorbornyl, etc.

Examples of the aforementioned aryl group having 6 to 12 carbon atoms include those obtained by removing two hydrogen atoms from the specific examples of the aforementioned aryl group having 6 to 12 carbon atoms, such as phenyl group and naphthyl group. , Biphenylene, etc.

As the alkylene group having 1 to 10 carbon atoms, the same as those exemplified in the description of ^{Q 2 above can be cited.} In the present invention, the alkylene group having 1 to 5 carbon atoms is preferable, the methylene group and the ethylene group are more preferable, and the methylene group is still more preferable.

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

Examples of the repeating unit represented by the formula (b) include those represented by the following formulas (b-1) to (b-16), but it is not limited to these. In addition, the following formulas, R ^A and the same line.

Examples of the repeating unit represented by the formula (c) include those represented by the following formulas (c-1) to (c-13), but are not limited to these. In addition, the following formulas, R ^A and the same line.

Examples of the repeating unit represented by the formula (d) include those represented by the following formulas (d-1) to (d-8), but it is not limited to these. In addition, the following formulas, R ^A and the same line.

(D) The polymer additive contains the repeating unit represented by the formula (a1), the repeating unit represented by the formula (b), and the repeating unit represented by the formula (c), wherein the repeating unit represented by the formula (b) In the hydroxyalkyl group, when the carbon atom to which the hydroxyl group is bonded is a second or third carbon atom (hereinafter, such a polymer additive is referred to as polymer additive D1.), formula (a1) The content of the repeating unit indicated is preferably 30-60 mol%, more preferably 35-50 mol% in the total repeating unit. The content rate of the repeating unit represented by the formula (b), in the total repeating unit, is preferably 10 to 35 mol%, more preferably 15 to 30 mol%. The content rate of the repeating unit represented by the formula (c), in the total repeating unit, is preferably 5-60 mol%, more preferably 20-50 mol%.

(D) The polymer additive contains the repeating unit represented by the formula (a1), the repeating unit represented by the formula (b), and the repeating unit represented by the formula (c), wherein the repeating unit represented by the formula (b) In the hydroxyalkyl group, when the carbon atom to which the hydroxyl group is bonded is the first-order carbon atom (hereinafter, such a polymer additive is referred to as polymer additive D2.), the repeating unit represented by formula (a1) The content of the total repeating unit is preferably 15-60 mol%, more preferably 25-60 mol%, still more preferably 30-60 mol%, and still more preferably 35-50 mol% Ear%. The content rate of the repeating unit represented by the formula (b), in the total repeating unit, is preferably 8 to 38 mol%, more preferably 10 to 38 mol%, and still more preferably 10 to 35 mol%, More preferably, it is 15~30 mole%. The content rate of the repeating unit represented by the formula (c), in the total repeating unit, is preferably 2 to 77 mol%, more preferably 2 to 65 mol%, and still more preferably 5 to 60 mol%, It is even better to be 20-50 mol%.

(D) When the polymer additive contains 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 repeating unit represented by the formula (d) ( Hereinafter, such a polymer additive is referred to as polymer additive D3.), the content of the repeating unit represented by the formula (a2), in the total repeating unit, is preferably 2 to 45 mol%, more preferably 5 ~35 mol%. The content rate of the repeating unit represented by the formula (b) is preferably 20 to 35 mol%, more preferably 25 to 35 mol% in the total repeating unit. The content of the repeating unit represented by the formula (c) is preferably 30 to 45 mol%, more preferably 35 to 45 mol% in the total repeating unit. The content rate of the repeating unit represented by the formula (d), in the total repeating unit, is preferably 5-18 mol%, more preferably 5-15 mol%.

(D) The Mw of the polymer additive is preferably 2,000 to 10,000, more preferably 3,000 to 6,000. Moreover, its Mw/Mn 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 3-100 parts by mass relative to 100 parts by mass of the polyurea of the component (A), but is more preferably 3 to 80 parts by mass, and still more preferably 3-50 parts by mass. 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 be repelled during film formation.

Here, when the (D) polymer additive is the polymer additive D1, its content is preferably 10-100 parts by mass, more preferably 20-100 parts by mass relative to 100 parts by mass of the polyurea of component (A), More preferably, it is 30-100 parts by mass. In addition, when the polymer additive (D) is polymer additive D2 or polymer additive D3, its content is preferably 5 to 80 parts by mass, more preferably 5 to 80 parts by mass relative to 100 parts by mass of polyurea of component (A). 50 parts by mass. (D) The polymer additive system may be used individually by 1 type, and may be used in combination of 2 or more types.

[(E) Solvent] The composition system for forming a release layer of the present invention contains a solvent as the (E) component. As the aforementioned solvents, glycol ether solvents with 3 to 20 carbons, ester solvents with 3 to 20 carbons, ketone solvents with 3 to 20 carbons, amide solvents with ether bonds are preferred, or Cyclic compound solvents with 3 to 20 carbon atoms.

As said glycol ether solvent, propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether, propylene glycol monopropyl ether, etc. are mentioned. Examples of the aforementioned amide-based solvents having ether linkages include 3-methoxy N,N dimethylpropionamide, 3-butoxy N,N dimethylpropionamide, and the like. Examples of the ester solvent include ethyl lactate, γ-butyrolactone, methyl 2-hydroxyisobutyrate, ethyl 2-hydroxyisobutyrate, and the like. Examples of the ketone solvent include methyl ethyl ketone, cyclohexanone, cyclopentanone, benzophenone, and the like. Examples of the cyclic compound solvent include γ-butyrolactone and the like.

(E) The content of the solvent is preferably such that the solid content concentration in the composition for forming a release layer of the present invention is 0.1-40% by mass, more preferably 0.5-20% by mass, and still more preferably The amount is 0.5-10% by mass. In addition, the term "solid content" refers to the general term for substances other than the solvent among all the components of the composition for forming a release layer. (E) The solvent system may be used individually by 1 type, and may mix and use 2 or more types.

[Other additives] The composition for forming a release layer of the present invention may contain a surfactant as needed. By adding a surfactant, the coating property of the composition for forming a release layer to a substrate can be improved. As the aforementioned surfactant, conventional surfactants such as nonionic surfactants, fluorine-based surfactants, and silicone-based surfactants can be used.

As specific examples of the aforementioned nonionic surfactants, for example, polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, polyoxyethylene oleyl ether, etc. can be mentioned. Polyoxyethylene alkyl ethers; polyoxyethylene alkyl aryl ethers such as polyoxyethylene octyl phenyl ether and polyoxyethylene nonyl phenyl ether; polyoxyethylene·polyoxypropylene block copolymers; Sorbitan monolaurate, sorbitan monopalmitate, sorbitan monofatty acid ester, sorbitan monooleate, sorbitan trioleate, sorbitan three Sorbitan fatty acid esters such as fatty acid esters; polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan mono Polyoxyethylene sorbitan fatty acid esters such as oxyethylene sorbitan trioleate and polyoxyethylene sorbitan tri fatty acid ester.

Examples of the aforementioned fluorine-based surfactants include Eftop (registered trademark) EF301, EF303, EF352 (manufactured by Mitsubishi Materials Electronics Co., Ltd.), Megafac (registered trademark) F171, F173, F554, F559, F563, R -30, R-30N, R-40, R-40-LM, DS-21 (DIC (stock) system), FLUORAD (registered trademark) FC430, FC431 (3M company system), AsahiGuard (registered trademark) AG710, Surflon (Registered trademark) S-382, SC101, SC102, SC103, SC104, SC105, SC106 (Asahi Glass Co., Ltd.), etc.

In addition, as the polysiloxane-based surfactant, organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.) and the like can be mentioned.

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

[Preparation of composition for forming peeling layer] The preparation method of the composition for forming a release layer of the present invention is not particularly limited. As a preparation method, for example, a solution of (A) component dissolved in a solvent and mixing (B) component, (C) component, (D) component, and (E) component at a specific ratio in a solution to make uniform The solution method, or in the appropriate stage of the aforementioned preparation method, further adding other additives and mixing as necessary.

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

In addition, the prepared solution of the composition for forming a peeling layer is preferably filtered using a filter with a pore size of about 0.2 μm or the like before use.

The viscosity of the composition for forming a release layer of the present invention is set appropriately after considering the thickness of the release layer to be produced, etc. However, especially when the purpose is to obtain a film with a thickness of about 0.01 to 5 μm with good reproducibility, Generally, it is about 1 to 5,000 mPa·s at 25°C, preferably about 1 to 2,000 mPa·s.

Here, the viscosity is a viscometer for measuring the viscosity of a commercially available liquid. For example, it can be measured under the condition that the temperature of the composition is 25°C by referring to the procedure described in JIS K7117-2. It is better to use a cone-plate type (cone-plate type) rotary viscometer as a viscometer, preferably a viscometer of the same type, use 1°34'×R24 as a standard cone rotor, and the temperature of the composition is 25°C Perform the measurement. As such a rotational viscometer, for example, TVE-25L manufactured by Toki Sangyo Co., Ltd. can be cited.

[Peeling layer] The composition for forming a release layer of the present invention is coated on a substrate and then is sintered at 180 to 250°C by a sintering method, thereby obtaining excellent adhesion to the substrate and adhesion to the resin substrate. A peeling layer with moderate adhesion and moderate releasability.

Although the heating time is different depending on the heating temperature, it cannot be specified in general, but it is usually 1 minute to 5 hours. In addition, if the maximum temperature of the temperature during the sintering is within the aforementioned range, the sintering step performed below the temperature may also be included.

As a preferable example of the heating aspect in the present invention, it can be cited as heating at 50~150℃ for 1 minute~1 hour, directly increasing the heating temperature, heating at 180~250℃ for 5 minutes~4 hours The state. In particular, a better example of the heating state can be a state of heating at 50 to 150°C for 1 minute to 1 hour, and heating at 200 to 250°C for 5 minutes to 2 hours. In addition, as a better other example of the heating state, it can be exemplified by 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.

In addition, when the peeling layer of the present invention is formed on a substrate, the peeling layer may be formed on a part of the surface of the substrate, or it may be formed on the entire surface. As a form of forming a peeling layer on a part of the surface of the substrate, there are forms of forming a peeling layer only in a specific area on the surface of the substrate, and patterns such as dot patterns, line and gap patterns, etc. on the entire surface of the substrate. The state of forming a peeling layer, etc. In addition, in the present invention, the so-called substrate means a composition for forming a release layer of the present invention is coated on the surface thereof and can be used in the manufacture of flexible electronic devices and the like.

As the matrix (substrate), for example, alkali glass is preferred. Examples of the soda glass include soda lime glass, borosilicate glass, and the like. From the viewpoint of price, soda lime glass is preferred. In addition, the surface of the substrate may be composed of a single material, or may be composed of two or more materials. As an aspect in which the surface of the substrate is composed of two or more kinds of materials, some areas of the surface of the substrate are made of certain materials, and the other surfaces are made of other materials. Patterns, line and gap patterns, and other pattern-like materials exist in other materials, etc.

The coating method is not specifically limited, but for example, cast coating method, spin coating method, knife coating method, dip coating method, roller coating method, bar coating method, die coating method, inkjet Method, printing method (relief, intaglio, lithography, screen printing, etc.) etc.

Examples of appliances used for heating include hot plates, ovens, and the like. The heating environment can be under air or under inert gas, and can be carried out under normal pressure or under reduced pressure.

The thickness of the peeling layer is usually about 0.01~50μm. From the viewpoint of productivity, it is preferably about 0.01~20μm, more preferably about 0.01~5μm. The thickness of the coating film before heating can be adjusted to achieve the desired The desired thickness.

The peeling layer of the present invention has excellent adhesion to the substrate, especially to the substrate of glass, and moderate adhesion and moderate releasability to the resin substrate. Therefore, the peeling layer of the present invention does not cause damage to the resin substrate of the device during the manufacturing process of the flexible electronic device, so it can be suitably used for the resin substrate and the circuit formed on the resin substrate, etc. When peeling from the substrate at the same time.

[Manufacturing method of resin substrate] An example of a manufacturing method of a flexible electronic device using the peeling layer of the present invention will be described. First, using the composition for forming a peeling layer of the present invention, a peeling layer is formed on a glass substrate by the aforementioned method. The resin substrate forming solution for forming the resin substrate is coated on the release layer, and the obtained coating film is sintered, and the resin substrate fixed to the glass substrate is formed through the release layer of the present invention.

The sintering temperature of the aforementioned coating film is appropriately set according to the type of resin, etc. However, in the present invention, it is preferable to set the maximum temperature during sintering to 200 to 250°C, more preferably to 210 to 250°C. It is better to set it at 220~240℃. By setting the maximum temperature during sintering during the production of the resin substrate within this range, the adhesion between the peeling layer of the base and the substrate, and the appropriate adhesion and peeling between the peeling layer and the resin substrate can be further improved. In the same case, as long as the maximum temperature is within the aforementioned range, a sintering step performed at a temperature lower than this temperature may also be included.

The resin substrate covers the entire peeling layer and forms the resin substrate with a larger area than the peeling layer. Examples of the resin substrate include a resin substrate composed of acrylic polymer or a resin substrate composed of cycloolefin polymer. The formation method of the resin substrate can be carried out according to a common method. In addition, as the aforementioned resin substrate, one having a light transmittance of 80% or more at a wavelength of 400 nm is preferable.

Next, on the resin substrate fixed to the base through the peeling layer of the present invention, the desired circuit is formed as required, and then the resin substrate is cut along the peeling layer, and the circuit and the resin substrate are simultaneously separated from the peeling layer. Peeling separates the resin substrate from the base. At this time, a part of the base body and the release layer may be simultaneously cut. If the peeling layer of the present invention is used, the resin substrate can be peeled by the peeling layer with a peeling force of 0.2N/25mm or less. In particular, when the polymer additive (D) is the polymer additive D2 or the polymer additive D3, the resin substrate can be peeled off by the peeling layer with a peeling force of 0.15N/25mm or less. In addition, when the polymer additive (D) is the polymer additive D1, the resin substrate can be peeled off by the peeling layer with a peeling force of 0.1N/25mm or less. [Example]

Hereinafter, a synthesis example, a preparation example, an example, and a comparative example are given to illustrate the present invention in further detail, but the present invention is not limited by the following examples.

The compounds used in the following examples are as follows. PGME: Propylene glycol monomethyl ether PGMEA: Propylene Glycol Monomethyl Ether Acetate NMP: N-methylpyrrolidone PL-LI: 1,3,4,6-Tetra (methoxyethyl) glycoluril (manufactured by ALLNEX, trade name: POWDERLINK 1174) BPDA: Biphenyl dianhydride PDA: p-phenylenediamine PPTS: P-pyridinium tosylate PHA: Phosphomolybdic acid hydrate HPMA: 2-hydroxypropyl methacrylate HEMA: 2-hydroxyethyl methacrylate ADMA: 2-adamantyl methacrylate CHMI: Cyclohexylmaleimide HFiPMA: 1,1,1,3,3,3-hexafluoroisopropyl methacrylate PFHMA: 2-(perfluorohexyl) ethyl methacrylate HADM: 3-hydroxy-1-adamantyl methacrylate DHADM: 3,5-dihydroxy-1-adamantyl methacrylate AIBN: Azobisisobutyronitrile

In addition, the weight average molecular weight (Mw) of the polymer was measured using a GPC device manufactured by JASCO Corporation (columns: Shodex (registered trademark) KD801 and KD805 (manufactured by Showa Denko Corporation)); eluent: dimethyl Formamide/LiBr·H ₂ O(29.6mM)/H ₃ PO ₄ (29.6mM)/THF(0.1% by mass); flow rate: 1.0mL/min; column temperature: 40°C; Mw: standard polystyrene Converted value) to proceed.

[1] Synthesis of polymers [Synthesis example 1] Synthesis of polyurea (L1) Dissolve 100 g of monoallyl diglycidyl isocyanuric acid (manufactured by Shikoku Chemical Co., Ltd.), 66.4 g of 5,5-diethylbarbituric acid, and 4.1 g of benzyltriethylammonium chloride After 682 g of propylene glycol monomethyl ether, 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) HFiPMA2.01g, HADM2.01g, ADMA2.50g, and AIBN0.23g were dissolved in PGME28.2g and reacted at 70°C for 20 hours to obtain an acrylic polymer (S1) solution (solid content concentration 20% by mass). The composition ratio of each unit is HFiPMA: HADM: ADMA = 30: 30: 40. As a result of GPC analysis, the obtained acrylic polymer (S1) had Mw of 5,240 and Mw/Mn of 1.8.

[Synthesis example 3] Synthesis of acrylic polymer (S2) HFiPMA 2.86 g, HADM 1.07 g, ADMA 3.00 g, and AIBN 0.25 g were dissolved in 29.9 g of PGME and reacted at 70° C. for 20 hours to obtain an acrylic polymer (S2) solution (solid content concentration 20% by mass). The composition ratio of each unit is HFiPMA: HADM: ADMA=40:15:45. As a result of GPC analysis, the obtained acrylic polymer (S1) had Mw of 5,080 and Mw/Mn of 1.8.

[Synthesis example 4] Synthesis of acrylic polymer (S3) HFiPMA 2.38 g, DHADM 0.95 g, ADMA 2.50 g, and AIBN 0.21 g were dissolved in PGME 25.2 g, and reacted at 70° C. for 20 hours to obtain an acrylic polymer (S2) solution (solid content concentration 20% by mass). The composition ratio of each unit is HFiPMA:DHADM:ADMA=40:15:45. As a result of GPC analysis, the obtained acrylic polymer (S1) had Mw of 4,740 and Mw/Mn of 1.8.

[Synthesis Example 5] Synthesis of acrylic polymer (S4) HFiPMA4.02g, HPMA2.22g, ADMA5.00g, and AIBN0.47g were dissolved in PGME49.1g, and it was made to react at 70 degreeC for 20 hours, and the acrylic polymer (S1) solution (solid content concentration 20 mass %) was obtained. The composition ratio of each unit is HFiPMA:HPMA:ADMA=30:30:40. As a result of GPC analysis, the obtained acrylic polymer (S1) had Mw of 5,040 and Mw/Mn of 1.7.

[Synthesis example 6] Synthesis of polyamide acid (S5) 3.218 g (30 mmol) of p-PDA was dissolved in 88.2 g of NMP. 8.581 g (29 mmol) of BPDA was added to the obtained solution, and it was allowed to react at 23° C. for 24 hours under a nitrogen environment to obtain polyamide S5. Polyamide S5 has Mw of 107,300 and Mw/Mn of 4.6.

[Preparation example 1] Preparation of composition F1 for resin substrate formation In an eggplant-shaped flask in which 100 g of carbon tetrachloride was placed, 10 g of ZEONOR (registered trademark) 1020R (cycloolefin polymer made by Zeon Co., Ltd.) and 3 g of EPOLEAD (registered trademark) GT401 (made by Daicel Co., Ltd.) were added. This solution was stirred and dissolved in a nitrogen atmosphere for 24 hours to prepare composition F1 for forming a resin substrate.

[Preparation example 2] Preparation of composition F2 for resin substrate formation In an eggplant-shaped flask containing 100 g of carbon tetrachloride, 10 g of ZEONOR (registered trademark) 1060R (cycloolefin polymer manufactured by Zeon Co., Ltd., Japan) was added. This solution was stirred in a nitrogen atmosphere for 24 hours to dissolve it, and the composition F2 for resin substrate formation was prepared.

[2] Preparation of composition for forming peeling layer [Example 1-1] Preparation of composition 1 for forming peeling layer To 1 g of the reaction liquid obtained in Synthesis Example 1, 0.06 g of PL-LI, 0.15 g of PPTS, 0.08 g of acrylic polymer (S1) solution, and PGMEA were added so that the solid content concentration was 5% by mass, and the PGMEA concentration was 30. The mass% was diluted with PGME to prepare composition 1 for forming a peeling layer.

[Example 1-2] Preparation of composition 2 for forming peeling layer Except having used the acrylic polymer (S2) solution instead of the acrylic polymer (S1) solution, the composition 2 for peeling layer formation was prepared by the method similar to Example 1-1.

[Example 1-3] Preparation of composition 3 for forming peeling layer Except having used the acrylic polymer (S3) solution instead of the acrylic polymer (S1) solution, the composition 3 for peeling layer formation was prepared by the method similar to Example 1-1.

[Example 1-4] Preparation of composition 3 for forming peeling layer Except having used the acrylic polymer (S4) solution instead of the acrylic polymer (S1) solution, the composition 4 for peeling layer formation was prepared by the method similar to Example 1-1.

[Comparative Example 1-1] Preparation of composition 4 for forming peeling layer (using phosphomolybdic acid) To 1 g of the reaction solution obtained in Synthesis Example 1, 0.04 g of PL-LI, 0.15 g of PHAS, 0.05 g of acrylic polymer (S4) solution, and PGMEA were added so that the solid content concentration was 1% by mass and the PGMEA concentration was 30 The mass% was diluted with PGME to prepare composition 5 for forming a peeling layer.

[Comparative Example 1-2] Preparation of Composition 5 for Forming Release Layer The polyamide acid (S5) solution was adjusted to a concentration of 5% by mass with NMP to prepare a composition 6 for forming a peeling layer.

[3] Production of peeling layer and resin substrate [Example 2-1] Using a spin coater (condition: a rotation speed of 1,000 rpm for about 30 seconds), the composition 1 for forming a peeling layer was coated on an alkali glass substrate (100 mm×100 mm, the same for all the following). The obtained coating film was heated at 100°C for 2 minutes using a hot plate, and then heated at 230°C for 10 minutes using a hot plate, and a peeling layer with a thickness of about 0.1 μm was formed on the alkali glass substrate to obtain a glass substrate with a peeling layer. Immediately after that, using a spin coater (condition: rotation speed 200 rpm for about 15 seconds), the resin substrate forming composition F1 was applied on the release layer (resin film) on the glass substrate. The obtained coating film was 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 with a thickness of about 3 μm on the release layer to obtain a glass substrate with a resin substrate and a release layer . After that, using an ultraviolet visible spectrophotometer (UV-2600 manufactured by Shimadzu Corporation) to measure the light transmittance, the resin substrate showed a transmittance of more than 90% at 400nm.

[Example 2-2] Except that the composition 2 for forming a peeling layer was used instead of the composition 1 for forming a peeling layer, a peeling layer and a resin substrate were produced in the same manner as in Example 2-1 to obtain an alkali glass substrate with a peeling layer and a resin substrate with peeling Layer of glass substrate.

[Example 2-3] Except that the composition F2 for forming a resin substrate was used instead of the composition F1 for forming a resin substrate, a peeling layer and a resin substrate were produced in the same manner as in Example 2-2 to obtain an alkali glass substrate with a peeling layer and a resin substrate with peeling Layer of alkali glass substrate. After that, using an ultraviolet visible spectrophotometer (UV-2600 manufactured by Shimadzu Corporation) to measure the light transmittance, the resin substrate showed a transmittance of more than 90% at 400nm.

[Example 2-4] Except that the release layer forming composition 3 was used instead of the release layer forming composition 1, a release layer and a resin substrate were produced in the same manner as in Example 2-1 to obtain a glass substrate with a release layer, a resin substrate and a release layer The glass substrate.

[Example 2-5] Except that the release layer forming composition 4 was used instead of the release layer forming composition 1, a release layer and a resin substrate were produced in the same manner as in Example 2-1 to obtain a glass substrate with a release layer, a resin substrate and a release layer The glass substrate.

[Comparative Example 2-1] Except that the composition 4 for forming a release layer was substituted for the composition 1 for forming a release layer, a release layer and a resin substrate were produced in the same manner as in Example 2-1 to obtain a glass substrate with a release layer, a resin substrate and a release layer The glass substrate.

[Comparative Example 2-2] Using a spin coater (condition: a rotation speed of 3,000 rpm for about 30 seconds), the composition 5 for forming a peeling layer was coated on an alkali glass substrate (100 mm×100 mm, the same for the following). The obtained coating film was heated at 100°C for 2 minutes using a hot plate, and then heated at 230°C for 60 minutes using a hot plate, and a peeling layer with a thickness of about 0.1 μm was formed on the alkali glass substrate, and a glass substrate with a peeling layer was obtained . Immediately after that, using a spin coater (condition: rotation speed 200 rpm for about 15 seconds), the resin substrate forming composition F1 was applied on the release layer (resin film) on the glass substrate. The obtained coating film was 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 with a thickness of about 3 μm on the release layer to obtain a glass substrate with a resin substrate and a release layer .

[4] Evaluation of peelability With respect to the glass substrates with a resin substrate and a peeling layer obtained in the foregoing Examples 2-1 to 2-4 and Comparative Examples 2-1 to 2-4, the peelability of the peeling layer and the glass substrate was confirmed by the following method. In addition, the following tests were performed on the same glass substrate.

(1) Evaluation of peelability between peeling layer and glass substrate Cross-cut the peeling layer on the glass substrate with peeling layer obtained in Examples 2-1~2-4 and Comparative Examples 2-1~2-4 (the interval is 2mm in both vertical and horizontal directions, and the following are the same), and 25 pieces Block cut. That is, by this cross cutting, 25 2mm square grids are formed. The tape was adhered to the 25 cut parts, and the tape was peeled off, and the degree of peeling was evaluated based on the following criteria. The results are shown in Table 1. <Judgment Criteria> 5B: 0% peeling (no peeling) 4B: Stripping of less than 5% 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 less than 95% peeling A: 95% to less than 100% peeling AA: 100% peeling (all peeling)

(2) Evaluation of peeling force between peeling layer and resin substrate On the glass substrates with resin substrates and peeling layers obtained in Examples 2-1 to 2-4 and Comparative Examples 2-1 to 2-4, a strip of 25 mm×50 mm was produced. After further pasting the transparent tape (registered trademark) (CT-24 manufactured by NICHIBAN), use the universal testing machine AGS-X500N (made by Shimadzu Corporation) at a peeling angle of 90° and a peeling speed of 300mm/min. Peel off, and measure the peel force based on the following criteria. AAA: 0.2N/25mm or less AA: 0.3~0.2N/25mm A: Above 0.3N/25mm ×: not peeled off

According to the results shown in Table 1, it was confirmed that the peeling layer of the example had excellent adhesion to the alkali glass substrate and was easily peeled from the resin film. Also, confirm that there is no change in the peeling force caused by the standby placement. On the other hand, it was confirmed that although the adhesion between Comparative Example 2-1 and the alkali glass substrate was excellent, the peelability with the resin substrate was not good, and the adhesion between Comparative Example 2-2 and the alkali glass substrate was poor, and the adhesion with the resin The substrate also has no peelability.

Claims (10)

A composition for forming a peeling layer for alkali glass, which contains the following components (A) to (E) and is coated on an alkali glass substrate and then sintered at a temperature of 300°C or less. When in contact with an organic thin film Below, it has a peeling force of 0.2N/25mm or less, (A) a polyurea containing the repeating unit represented by the following formula (1), (B) a sulfonic acid compound or its salt, (C) is composed of a hydroxyalkyl group And/or a crosslinking agent selected from a compound having a nitrogen atom substituted by an alkoxymethyl group, (D) comprising a repeating unit represented by the following formula (a1), a repeating unit represented by the following formula (b), and The polymer additive of the repeating unit represented by the following formula (c): 3-100 parts by mass relative to 100 parts by mass of (A) polyurea, (E) solvent

[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, and X ¹ is 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 with 1 to 6 carbons, an alkenyl group with 3 to 6 carbons, a benzyl group, or a phenyl group. ~6 alkyl group, halogen atom, C1-C6 alkoxy group, nitro group, cyano group, hydroxyl group and C1-C6 alkylthio group selected by at least one group substituted, and , R ¹ and R ² can also be bonded to each other, and together with these bonded carbon atoms form a ring with carbon number of 3-6, R ³ is an alkyl group with carbon number of 1 to 6, and a carbon number of 3-6 Alkenyl, benzyl, or phenyl. The aforementioned phenyl group can also be composed of an alkyl group with 1 to 6 carbons, a halogen atom, an alkoxy group with 1 to 6 carbons, a nitro group, a cyano group, a hydroxyl group, and a carbon number of 1~ At least one group selected from the group of 6 alkylthio groups); 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 formula (1-1), formula (1-2) or formula (1-4), and Q ² is an alkylene group, phenylene group, and a Naphthyl or anthrylene, the aforementioned phenyl, naphthyl, and anthracenyl groups can also be composed of alkyl groups with 1 to 6 carbon atoms, halogen atoms, alkoxy groups with 1 to 6 carbon atoms, nitro groups, and cyano groups. , Hydroxyl, and at least one group selected from the group of alkylthio groups with 1 to 6 carbon atoms, 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, R ^B1 is a branched alkyl group with 3 or 4 carbon atoms in which at least one hydrogen atom is replaced by a fluorine atom, and R ^C has a carbon number of 2-10 The hydroxyalkyl group or the polycyclic alkyl group of 6-20 carbons with 1 to 4 hydroxy groups, R ^D is a polycyclic alkyl group with 6-20 carbons or an aryl group with 6-12 carbons). The composition for forming a peeling layer for alkali glass as described in claim 1, wherein, in the repeating unit represented by formula (b) of (D) polymer additive, R ^C is a hydroxyalkyl group having a carbon number of 2 to 10 Or 1 to 4 hydroxyl groups and a polycyclic alkyl group with 6 to 20 carbon atoms, in which the carbon atom to which the hydroxyl group is bonded is the second or third carbon atom, and the repetition represented by the formula (a1) The content ratio of the units is 20 mol% or more and 80 mol% or less in the total repeating units of the (D) polymer additive. The composition for forming a peeling layer for alkali glass as described in claim 1 or 2, wherein X ¹ is a group represented by formula (1-3). The composition for forming a peeling layer for alkali glass as described in claim 3, wherein R ³ is a 2-propenyl group. The composition for forming a peeling layer for alkali glass as described in any one of claims 1 to 4, wherein Q ¹ is a group represented by formula (1-5). The composition for forming a peeling layer for alkali glass as described in any one of claims 1 to 5, wherein the (C) crosslinking agent is any of the following formulas (C-1) to (C-7) Compound represented by one:

(In the formula, R ¹¹ to R ³⁸ are each independently a hydrogen atom or an alkyl group with 1 to 6 carbon atoms, and R ³⁹ is a hydrogen atom or a methyl group). In the composition for forming a peeling layer for alkali glass as described in any one of claims 1 to 6, the content of the (C) crosslinking agent is 10 to 100 parts by mass relative to 100 parts by mass of the (A) polyurea. A peeling layer obtained from the composition for forming a peeling layer for alkali glass as described in any one of claims 1 to 7. A laminated body which is laminated on the release layer as described in claim 8 and laminated with a resin layer with a light transmittance of 80% or more at a wavelength of 400 nm. A method for manufacturing a resin substrate, which includes: The step of applying the composition for forming a peeling layer for alkali glass as described in any one of claims 1 to 7 on a substrate to form a peeling layer, The step of forming a resin substrate with a light transmittance of 80% or more at a wavelength of 400 nm on the aforementioned release layer, and The step of peeling the aforementioned resin substrate with a peeling force of 0.2N/25mm or less.