TW202045587A - Composition for forming release layer for slit die coating, and release layer - Google Patents

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 DEG 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 coating and release layer

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

In recent years, in addition to the characteristics of thinner and lighter weight, electronic devices are also required to be flexible. Therefore, it is sought to use a lightweight flexible plastic substrate to replace the heavy and fragile glass substrate that cannot be bent in the past.

In particular, in the new generation of displays, it is sought to develop active matrix full-color TFT display panels using a lightweight flexible plastic substrate (hereinafter also referred to as a resin substrate). In addition, touch-sensitive displays have developed materials that correspond to flexible materials such as transparent electrodes or resin substrates of touch panels used in combination with display panels. As transparent electrodes, ITO has been used since the past, and other transparent electrode materials such as PEDOT and other bendable transparent conductive polymers, metal nanowires and their hybrid systems have been proposed (Patent Documents 1 to 4).

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

Generally, a flexible touch screen panel is produced by making a peeling layer (adhesive layer) on a supporting substrate such as a glass substrate for stable production and peeling, and then peeling off after manufacturing a device on it (Patent Document 8). The peeling layer needs to not peel from the supporting substrate during the stroke, but on the other hand, it has a low peeling force during peeling.

In addition, in recent years, the slit coating method has been used on the production line from the viewpoint of suppressing the use of the coating liquid and simplifying the accompanying steps of productivity (Patent Documents 9, 10). This method is different from the spin coating method. Since the film contains a large amount of solvents after film formation, a vacuum drying process is required. This process is implemented between coating treatment and heating treatment, and is necessary to stabilize the unstable film just after coating. However, coating unevenness may occur due to the influence of residual solvents caused by reduced pressure, so it is necessary to improve the unevenness of coating. [Prior Technical Literature] [Patent Literature]

[Patent Document 1] International Publication No. 2012/147235 [Patent Document 2] JP 2009-283410 A [Patent Document 3] JP 2010-507199 Publication [Patent Document 4] JP 2009-205924 A [Patent Document 5] International Publication No. 2017/002664 [Patent Document 6] International Publication No. 2016/160338 [Patent Document 7] JP 2015-166145 A [Patent Document 8] JP 2016-531358 A [Patent Document 9] JP 2014-102490 A [Patent Document 10] JP 2014-106956 A

[The problem to be solved by the invention]

The present invention was completed in view of the foregoing circumstances, and its purpose is to provide a resin substrate with excellent adhesion to the substrate without causing uneven coating even when it is coated by a slit coating method. A composition for forming a release layer for slit coating of a release layer with moderate adhesion and moderate release. [Means to solve the problem]

The inventors of the present invention repeated the results of active reviews in order to achieve the above objectives, and found that they contain (A) polyurea containing specific repeating units, (B) acid compounds or salts thereof, (C) selected from hydroxyalkyl groups and/or A crosslinking agent for compounds with alkoxymethyl substituted nitrogen atoms, (D) polymer additives containing specific repeating units, and (E) stripping of solvents made of solvents whose vapor pressure is below 800 Pa at 20°C A composition for layer formation, which is excellent as a composition for slit coating, and reproducibly imparts a release layer with excellent adhesion to the substrate, moderate adhesion to the resin substrate, and moderate releasability , Thus completing the present invention.

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

(式中，R¹ 及R² 分別獨立為氫原子、碳數1~6之烷基、碳數3~6之烯基、苄基或苯基，前述苯基可經選自碳數1~6之烷基、鹵原子、碳數1~6之烷氧基、硝基、氰基、羥基及碳數1~6之烷硫基所成之群中之至少1種基取代，且R¹ 及R² 亦可相互鍵結與該等所鍵結之碳原子一起形成碳數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，前述苯基可經選自碳數1~6之烷基、鹵原子、碳數1~6之烷氧基、硝基、氰基、羥基及碳數1~6之烷硫基所成之群中之至少1種基取代)， Q¹ 為下述式(1-5)或(1-6)表示之基，

(式中，X² 為式(1-1)、式(1-2)或式(1-4)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、伸萘基及伸蒽基可經選自碳數1~6之烷基、鹵原子、碳數1~6之烷氧基、硝基、氰基、羥基及碳數1~6之烷硫基所成之群中之至少1種基取代，n¹ 及n² 分別獨立為0或1)]

(式中，R^A 分別獨立為氫原子或甲基，R^B1 係至少1個氫原子經氟原子取代之碳數3或4之分支狀烷基，R^C 係碳數1~10之羥基烷基，R^D 為碳數6~20之多環式烷基或碳數6~12之芳基)。 2. 如1之狹縫式塗佈用剝離層形成用組成物，其中(D)高分子添加物之式(b)表示之重複單位中，R^C 為碳數2~10之羥基烷基，羥基所鍵結之碳原子為2級碳原子，且式(a1)表示之重複單位之含有比例於(D)高分子添加物之全部重複單位中為30莫耳%以上。 3. 如1或2之狹縫式塗佈用剝離層形成用組成物，其中X¹ 為式(1-3)表示之基。 4. 如3之狹縫式塗佈用剝離層形成用組成物，其中R³ 為2-丙烯基。 5. 如1至4中任一項之狹縫式塗佈用剝離層形成用組成物，其中Q¹ 為式(1-5)表示之基。 6. 如1至5中任一項之狹縫式塗佈用剝離層形成用組成物，其中(B)成分係磺酸化合物或其鹽。 7. 如1至6中任一項之狹縫式塗佈用剝離層形成用組成物，其中(C)交聯劑為下述式(C-1)~(C-7)之任一者表示之化合物，

(式中，R¹¹ ~R³⁸ 分別獨立為氫原子或碳數1~6之烷基，R³⁹ 為氫原子或甲基)。 8. 如1至7中任一項之狹縫式塗佈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。 9. 一種剝離層，其係由如1至8中任一項之狹縫式塗佈用剝離層形成用組成物所得。 10. 一種層合體，其係於如9之剝離層上層合波長400nm之光透過率為80%以上之樹脂層而成。 11. 一種樹脂基板之製造方法，其包含 將如1至8中任一項之狹縫式塗佈用剝離層形成用組成物塗佈於基體上，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 以0.15N/25mm以下之剝離力剝離前述樹脂基板之步驟。 [發明效果]That is, the present invention provides the following composition for forming a release layer for slit coating and a release layer. 1. A composition for forming a release layer for slit coating, comprising (A) a polyurea containing a repeating unit represented by the following formula (1), (B) an acid compound or its salt, and (C) selected from A crosslinking agent of a compound having a hydroxyalkyl group and/or a nitrogen atom substituted with an alkoxymethyl group, (D) containing a repeating unit represented by the following formula (a1), a repeating unit represented by the following formula (b), and The polymer additive in the repeating unit represented by the following formula (c), and (E) a solvent containing at least one solvent with a vapor pressure of 800 Pa or less at 20°C, (D) the polymer additive is relative to (A) polyurea 100 parts by mass, containing 3~100 parts by mass,

[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 a carbon number of 1 to 6, an alkenyl group with a carbon number of 3 to 6, a benzyl group or a phenyl group. At least one of the group consisting of 6 alkyl groups, halogen atoms, C1-C6 alkoxy groups, nitro groups, cyano groups, hydroxyl groups and C1-C6 alkylthio groups, and R ¹ And R ² can also be bonded to each other together with the bonded carbon atoms to form a carbon 3-6 ring, R ³ is an alkyl with 1 to 6 carbons, an alkenyl with 3 to 6 carbons, and a benzyl group Or phenyl group, the aforementioned phenyl group can be selected from alkyl groups having 1 to 6 carbon atoms, halogen atoms, alkoxy groups having 1 to 6 carbon atoms, nitro groups, cyano groups, hydroxyl groups and alkylthio groups having 1 to 6 carbon atoms At least one group in the group 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, phenylene, or naphthalene with 1 to 10 carbon atoms The aforementioned phenylene, naphthylene and anthracene groups can be selected from alkyl groups with 1 to 6 carbons, halogen atoms, alkoxy groups with 1 to 6 carbons, nitro, cyano, Substitution of at least one group of hydroxyl group and alkylthio group with carbon number 1~6, n ¹ and n ² are independently 0 or 1)]

(In the formula, R ^{A is} independently a hydrogen atom or a methyl group, R ^B1 is a branched alkyl group with 3 or 4 carbons in which at least one hydrogen atom is replaced by a fluorine atom, and R ^C is a hydroxyalkane with 1 to 10 carbons. R ^D is a polycyclic alkyl group with 6 to 20 carbons or an aryl group with 6 to 12 carbons). 2. The composition for forming a release layer for slit coating as in 1, wherein in the repeating unit represented by formula (b) of (D) polymer additives, R ^C is a hydroxyalkyl group with 2 to 10 carbon atoms, The carbon atom to which the hydroxyl 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 in all the repeating units of the polymer additive (D). 3. The composition for forming a release layer for slit coating according to 1 or 2, wherein X ¹ is a base represented by formula (1-3). 4. The composition for forming a release layer for slit coating according to ³ , wherein R ³ is a 2-propenyl group. 5. The composition for forming a release layer for slit coating according to any one of 1 to 4, wherein Q ¹ is a base represented by formula (1-5). 6. The composition for forming a release layer for slit 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 coating according to any one of 1 to 6, wherein the (C) crosslinking agent is any of the following formulas (C-1) to (C-7) Represents the compound,

(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). 8. The composition for forming a release layer for slit coating according to any one of 1 to 7, wherein the content of (C) crosslinking agent is 10-100 mass parts relative to 100 mass parts of (A) polyurea Copies. 9. A peeling layer obtained from the composition for forming a peeling layer for slit coating according to any one of 1 to 8. 10. A laminated body, which is formed by laminating a resin layer with a light transmittance of 80% or more at a wavelength of 400 nm on a release layer such as 9. 11. A method of manufacturing a resin substrate, comprising the step of applying the composition for forming a peeling layer for slit coating as in any one of 1 to 8 on a substrate to form a peeling layer, on the peeling layer , A step of forming 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 0.15N/25mm or less. [Invention Effect]

By using the composition for forming a release layer for slit coating of the present invention, coating unevenness is not generated, and it has excellent adhesion to the substrate and moderate adhesion to the resin substrate with good reproducibility. And moderately peelable peeling layer. In the manufacturing process of the flexible electronic device, the resin substrate formed on the substrate or the circuit provided on the substrate is not damaged, and the circuit and the like can be separated from the substrate together with the resin substrate. Therefore, the composition for forming a release layer for slit coating of the present invention can contribute to the speeding up of the manufacturing process of flexible electronic devices provided with the resin substrate or the improvement of yield.

[Composition for forming release layer for slit coating]

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

[(A) Polyurea] The polyurea of the component (A) 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, but from the viewpoint of releasability and productivity, A ¹ to All A ⁶ are hydrogen atoms.

In 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 phenyl group can be selected from the group consisting of alkyl groups with 1 to 6 carbons, halogen atoms, alkoxy groups with 1 to 6 carbons, nitro, cyano, hydroxyl, and alkylthio groups with 1 to 6 carbons. At least one of the groups is substituted, and R ¹ and R ² may also be bonded to each other to form a carbon 3-6 ring together with the bonded carbon atoms.

In 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 can be selected from alkyls with 1 to 6 carbons. , Halogen atom, C1-C6 alkoxy group, nitro group, cyano group, hydroxyl group and C1-C6 alkylthio group are substituted with at least one group.

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

(式中，R¹ 及R² 與前述相同)。In formula (1-5), X ² is a group represented by formula (1-1), formula (1-2) or formula (1-4). In formula (1-5), for example, when X ² is a group represented by 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 described above).

In 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, naphthylene and anthracene groups can be selected from alkyl groups having 1 to 6 carbon atoms, halogen atoms, alkoxy groups having 1 to 6 carbon atoms, nitro groups, cyano groups, hydroxyl groups and carbon numbers 1~6. At least one of the group consisting 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, there may be cases where 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, and the naphthylene group is bonded at the 1-position and the 2-position. In the case of position bonding, the case of bonding with the 1-position and the 4-position, the case of the bonding with the 1-position and the 5-position, or the case of the 2-position and the 3-position bonding, the anthracene group is bonded with the 1-position and the 2-position It can be either the case, the case of bonding with 1 position and 4 positions, or the case of bonding with 9 positions and 10 positions.

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

The alkoxy group having 1 to 6 carbon atoms may be any of linear, branched, and cyclic, and examples include methoxy, ethoxy, isopropoxy, n-pentoxy and cyclohexyl. Oxy etc. The alkylthio group having 1 to 6 carbon atoms may be linear, branched, or cyclic, and examples include methylthio, ethylthio, isopropylthio, n-pentylthio, and cyclohexylthio. Base etc. Examples of the aforementioned halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and the like. In addition, examples of the ring having 3 to 6 carbon atoms formed by bonding R ¹ and R ² include a cyclobutane ring, a cyclopentane ring, and a cyclohexane ring.

The aforementioned alkylene group having 1 to 10 carbon atoms may be linear, branched, or cyclic, and examples include methylene, ethylene, propylene, pentamethylene, and ring extension. Hexyl, 2-methylpropylene, etc.

(式中，A¹ ~A⁶ 、R¹ ~R³ 及Q¹ 與前述相同)。Moreover, in formula (1), when X ¹ is a base represented by formula (1-2), its structure is represented by the following formula (2), and when X ¹ is a base represented by formula (1-3), The structure is represented by the following formula (3). In addition, in formula (3), R ^{3 is} preferably 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), based on the heat resistance of the polyurea of the component (A), Q ¹ preferably includes a cyclic structure. That is, it is preferable that 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 anthrylene group , More preferably a base represented by formula (1-5).

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

(A) The polyurea of component can refer to, for example, International Publication No. Synthesized under 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, the Mn coefficient is the average molecular weight, Mw and Mn are measured by gel permeation chromatography (GPC) converted from polystyrene.

[(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 component (B). Examples of the aforementioned acid compounds are p-toluenesulfonic acid, trifluoromethanesulfonic acid, pyridinium-p-toluenesulfonate, salicylic acid, camphorsulfonic acid, sulfosalicylic acid, 4-chlorobenzenesulfonic acid, 4 -Sulfonic acid compounds such as hydroxybenzenesulfonic acid, benzenedisulfonic acid, 1-naphthalenesulfonic acid, or carboxylic acid compounds such as salicylic acid, sulfosalicylic acid, citric acid, benzoic acid, and hydroxybenzoic acid. In addition, as the salt of the aforementioned acid compound, pyridinium salt, isopropanolamine salt, N-methylmorpholine salt, etc. of the aforementioned acid are exemplified, and specific examples are p-toluenesulfonic acid pyridinium salt, 1-naphthalenesulfonic acid pyridinium Onium salt, isopropanolamine p-toluenesulfonate, N-methylmorpholine p-toluenesulfonate, etc.

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 in the above range, a composition capable of imparting a peeling layer having heat resistance, moderate peelability, and excellent stability after film formation can be obtained. (B) An acid compound or its salt 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 component (C). The aforementioned crosslinking agent is selected from compounds having a hydroxyalkyl group and/or a nitrogen atom substituted with an alkoxymethyl group.

The crosslinking agent is preferably 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, but preferably an alkyl group having 1 to 6 carbon atoms. R ³⁹ is a hydrogen atom or a methyl group.

As the aforementioned crosslinking agent, specific examples are 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.

In addition, examples of the crosslinking agent are methoxymethyl melamine compounds (trade names CYMEL (registered trademark) 300, CYMEL 301, CYMEL 303, CYMEL 350) manufactured by ALLNEX, butoxymethyl melamine (trade name MYCOTE (registered 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, BECKAMINE P-955, BECKAMINE N) and other commercially available nitrogen-containing compounds.

In addition, as the crosslinking agent, 3,3'-5,5'-tetra(methoxymethyl)-[1,1'-biphenyl]-4,4'-diol, 5,5'- (1-Methylethylene)bis[2-hydroxy-1,3-benzenedimethanol] and other aromatic ring-containing compounds.

Furthermore, N-methylol (meth)acrylamide, N-methoxymethyl (meth)acrylamide, N-ethoxymethyl (meth)acrylamide, and N-ethoxymethyl (meth)acrylamide can be used as a crosslinking agent. Amine, N-butoxymethyl(meth)acrylamide, etc., are polymers produced by (meth)acrylamide compounds substituted with methylol or alkoxymethyl. Examples of such polymers include poly(N-butoxymethyl(meth)acrylamide), copolymer of N-butoxymethyl(meth)acrylamide and styrene, N-hydroxyl Copolymer of methyl(meth)acrylamide and methyl(meth)acrylate, copolymer of N-ethoxymethylmethacrylamide and benzyl methacrylate, N-butoxymethyl Copolymer of (meth)acrylamide, benzyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate, etc.

As the aforementioned crosslinking agent, more preferable examples are 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 by self-condensation. In addition, it can cause a crosslinking reaction with the hydroxyl group in the polyurea of component (A). Therefore, due to this crosslinking reaction, the formed release layer becomes strong and becomes a release layer with low solubility in organic solvents.

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

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

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. R ^C is a hydroxyalkyl group with 1 to 10 carbon atoms. R ^D is a polycyclic alkyl group with 6 to 20 carbons or an aryl group with 6 to 12 carbons.

The branched alkyl group having 3 or 4 carbon atoms is exemplified by isopropyl group, isobutyl group, second butyl group, and tertiary butyl group. R ^{B1 is} preferably one in which at least one hydrogen atom of the branched alkyl group is substituted with a fluorine atom. Specific examples include 1,1,1-trifluoroisopropyl, 1,1,1,3, 3,3-hexafluoroisopropyl, nonafluoro tertiary butyl, etc.

Examples of the aforementioned hydroxyalkyl group having 1 to 10 carbon atoms include hydroxymethyl, 2-hydroxyethyl, 3-hydroxypropyl, 4-hydroxybutyl, 5-hydroxypentyl, 6-hydroxyhexyl, and 7-hydroxyheptyl. Base, 8-hydroxyoctyl, 9-hydroxynonyl, 10-hydroxydecyl, 2-hydroxy-1-methylethyl, 2-hydroxy-1,1-dimethylethyl, 3-hydroxy-1 -Methylpropyl, 3-hydroxy-1,2-dimethylpropyl, 3-hydroxy-2,2-dimethylpropyl, 4-hydroxy-1-methylbutyl, 4-hydroxy-2 -Methylbutyl, 4-hydroxy-3-methylbutyl, and other hydroxyalkyl groups with 1 to 10 carbon atoms, and the carbon atom to which the hydroxyl group is bonded is a first-order carbon atom; 1-hydroxyethyl, 1 -Hydroxypropyl, 2-hydroxypropyl, 1-hydroxybutyl, 2-hydroxybutyl, 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 2-10 carbons, and the carbon atom to which the hydroxyl group is bonded is 2 Grade or grade 3 carbon atoms. R ^{C is} particularly preferably a hydroxyalkyl group having 2 to 10 carbon atoms and the carbon atom to which the hydroxyl group is bonded is a secondary carbon atom.

Examples of the aforementioned polycyclic alkyl group having 6 to 20 carbon atoms include 1-adamantyl, 2-adamantyl, isobornyl, and borneol. 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 contain 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 repeating unit represented by the following formula (d) Represents the repeated unit.

In the formula, R ^A , R ^C and R ^{D are the} same as 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 (except 2-methyl-1,1,1,3,3,3-hexafluoroisopropyl). Examples of the branched alkyl group having 3 or 4 carbon atoms are the same as those described above. R ^E 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 1-10 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 in which one hydrogen atom is removed from the specific example of the aforementioned polycyclic alkyl group having 6 to 20 carbon atoms. Examples are, for example, adamantyl group and alkylene group. Different borneol base, stretched borneol base, etc.

Examples of the aforementioned aryl group having 6 to 12 carbon atoms include a group having one hydrogen atom removed from the specific examples of the aforementioned aryl group having 6 to 12 carbon atoms, such as phenylene group, naphthylene group, and biphenylene group. .

As the alkylene having 1 to 10 carbon atoms, the same as those exemplified in the description of Q ² can be exemplified. 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) are those represented by the following formulas (a-1) to (a-3), but are not limited to these. In the following formula, R ^A is the same as described above.

As the repeating unit represented by the formula (b), those represented by the following formulas (b-1) to (b-16) are exemplified, but are not limited to these. In addition, in the following formula, R ^A is the same as described above.

As the repeating unit represented by the formula (c), those represented by the following formulas (c-1) to (c-13) are exemplified, but are not limited to these. In addition, in the following formula, R ^A is the same as described above.

As the repeating unit represented by the formula (d), those represented by the following formulas (d-1) to (d-8) are exemplified, but are not limited to these. In addition, in the following formula, R ^A is the same as described above.

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

(D) The polymer additive contains the repeating unit represented by formula (a1), the repeating unit represented by formula (b) and the repeating unit represented by formula (c), and among the repeating units represented by formula (b) When the carbon atom to which the hydroxyl group of the hydroxyalkyl group is bonded is a first-order carbon atom, the content of the repeating unit represented by formula (a1), in all repeating units, is preferably 15-60 mol%, more preferably 25-60 mol%, more preferably 30-60 mol%, still more preferably 35-50 mol%. The content rate of the repeating unit represented by formula (b) is preferably 8~38 mol%, more preferably 10~38 mol%, and still more preferably 10~35 mol% in all repeating units. More preferably, it is 15-30 mole%. The content rate of the repeating unit represented by formula (c) is preferably 2~77 mol%, more preferably 2~65 mol%, and more preferably 5~60 mol% in all repeating units. More preferably, it is 20-50 mole%.

(D) When the polymer additive contains the repeating unit represented by formula (a2), the repeating unit represented by formula (b), the repeating unit represented by formula (c), and the repeating unit represented by formula (d) , The content rate of the repeating unit represented by the formula (a2), in all repeating units, is preferably 2~45 mol%, more preferably 5~35 mol%. The content rate of the repeating unit represented by formula (b) is preferably 20 to 35 mol%, more preferably 25 to 35 mol% in all repeating units. The content rate of the repeating unit represented by formula (c) is preferably 30-45 mol%, more preferably 35-45 mol% in all repeating units. The content rate of the repeating unit represented by formula (d) is preferably 5-18 mol%, more preferably 5-15 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 is preferably 1.0 to 2.1, more preferably 1.0 to 1.9.

(D) The content of the polymer additive is 3 to 100 parts by mass, more preferably 3 to 80 parts by mass, and still more preferably 3 to 50 parts by mass relative to 100 parts by mass of polyurea of component (A). When the content of the polymer additive is less than 3 parts by mass, the peeling force may increase, and when it exceeds 100 parts by mass, it may be rejected during film formation. (D) The polymer additive may be used alone or in combination of two or more kinds.

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

Examples of the aforementioned glycol ether solvent include 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, ethyl acetate 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 Ether (Diglyme), 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, dipropylene glycol monoethyl ether acetate (DEGEEA), methoxymethyl butanol, tripropylene glycol dimethyl ether, triethylene glycol butyl methyl ether, etc.

Examples of the aforementioned ester solvent include ethyl acetate, butyl acetate, methoxybutyl acetate, amyl acetate, isopropyl acetate, methyl lactate, ethyl lactate (EL), butyl lactate, 2-hydroxy iso Methyl butyrate, ethyl 2-hydroxyisobutyrate, ethyl 3-methoxypropionate, etc.

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 aforementioned cyclic compound solvent include tetrahydrofuran, 1,4-dioxane, 1,3-dioxolane, 2-pyrrolidone, N-methylpyrrolidone (NMP), N-ethyl Pyrolidone (NEP), 1,3-dimethyl-2-imidazolidinone (DMI), γ-butyrolactone (GBL), etc.

The solvent of component (E) contains at least one solvent with a vapor pressure of 800 Pa or less at 20°C. The vapor pressure of the aforementioned solvent is preferably 700 Pa or less, more preferably 600 Pa or less from the viewpoint of volatility during drying under reduced pressure. The lower limit of the vapor pressure is not particularly limited, but it is usually 0.1 Pa or more, and preferably 0.5 Pa or more. As a solvent having a vapor pressure of 800 Pa or less, one having a vapor pressure of 800 Pa or less among the aforementioned solvents is preferable. As these solvents, 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 two Alcohol diethyl ether, ethylene glycol butyl methyl ether, Triglyme, 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, methyl 2-hydroxyisobutyrate, ethyl 2-hydroxyisobutyrate, ethyl 3-ethoxypropionate Esters, diacetone alcohol, cyclohexanone, 2-pyrrolidone, NMP, NEP, DMI, GBL, etc.

The content of the solvent with a vapor pressure of 800 Pa or less at 20°C, based on the viewpoint of non-volatility during drying under reduced pressure, the composition of the present invention is preferably 1 to 99.9 mass%, more preferably 1 to 90 mass% , And more preferably 5~80% by mass.

(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 becomes an amount of 0.1-40% by mass, more preferably an amount of 0.5-20% by mass, and still more preferably It becomes the amount of 0.5-10% by mass. In addition, the so-called solid part is a general term for all the components of the composition for forming a release layer except for the solvent. A solvent may be used individually by 1 type, and may be used in combination of 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.

Specific examples of the aforementioned nonionic surfactant include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, and polyoxyethylene oleyl ether; Polyoxyethylene alkyl aryl ethers such as oxyethylene octyl phenyl ether and polyoxyethylene nonyl phenyl ether; polyoxyethylene and polyoxypropylene block copolymers; sorbitan monolaurate, Sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, sorbitan tristearate, etc. Alkyd fatty acid esters; polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan Polyoxyethylene sorbitan fatty acid esters such as trioleate and polyoxyethylene sorbitan tristearate.

Examples of the aforementioned fluorine-based surfactants are EF TOP (registered trademark) EF301, EF303, EF352 (manufactured by Mitsubishi Materials Electronics Co., Ltd.), MEGAFAC (registered trademark) F171, F173, F554, F559, F563, R-30, 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 (made by Asahi Glass Co., Ltd.), etc.

In addition, the silicone-based surfactant is exemplified by organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.).

When the composition for forming a peeling layer contains a surfactant, its 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 surfactants may be used singly or in combination of two or more kinds.

[Preparation of a composition for forming a release layer for slit coating] The preparation method of the composition for forming a release layer for slit coating of the present invention is not particularly limited. An example of the preparation method is a method of mixing (B), (C), (D), and (E) in a solution of (A) component dissolved in a solvent in a specific ratio to make a uniform solution, or In the appropriate stage of the aforementioned preparation method, other additives are added and mixed as needed.

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 used as it is. In this case, for example, the (B) component is fed into the solution of the (A) component in the same manner as described above, and the (C) component, (D) component, (E) component, and the like are made into a uniform solution. In this case, the solvent can be added for the purpose of concentration adjustment. At this time, the solvent used in the production process of the component (A) and the solvent used in the concentration adjustment of the release layer forming composition may be the same or different.

In addition, the prepared solution of the composition for forming a peeling layer is preferably used after being filtered with a filter having a pore size of about 0.2 μm.

The viscosity of the composition for forming a release layer of the present invention can be appropriately set in consideration of the thickness of the release layer to be produced, but for the purpose of obtaining a film with a thickness of about 0.01 to 5 μm with good reproducibility, it is usually at 25°C It is about 1~5,000mPa･s, preferably about 1~2,000mPa･s.

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

[Peeling layer] It includes a step of applying the composition for forming a release layer for slit coating of the present invention on a substrate by a slit coating method using a slit coater, and then firing at 180~250°C The firing method can obtain a peeling layer with excellent adhesion to the substrate and moderate adhesion and moderate releasability to the resin substrate.

The heating time varies with the heating temperature and cannot be specified, but it is usually 1 minute to 5 hours. In addition, as long as the temperature at the time of the firing is the highest temperature in the above range, the firing step may be included at a temperature lower than that.

As a preferable example of the heating aspect of the present invention, for example, after heating at 50-150°C for 1 minute to 1 hour, the heating temperature is directly increased, and heating at 180-250°C for 5 minutes to 4 hours. In particular, as a better example of the heating state, for example, heating at 50~150°C for 1 minute to 1 hour, and 200~250°C for 5 minutes to 2 hours. Furthermore, as a more preferable example of the heating state, after heating at 50 to 150°C for 1 to 30 minutes, heating at 200 to 250°C for 5 minutes to 1 hour, for example.

In addition, when the release layer of the present invention is formed on a substrate, the release layer may be formed on a part of the surface of the substrate, or it may be formed on the entire surface. As an aspect of forming a peeling layer on a part of the surface of the substrate, for example, the aspect of forming a peeling layer only in a specific area on the surface of the substrate, and forming the entire surface of the substrate with patterns such as dot pattern, line and space pattern, etc. The state of the peeling layer, etc. In the present invention, the term "base system" where the composition for forming the release layer of the present invention is applied to the surface of the base system refers to those used in the manufacture of flexible electronic devices and the like.

Examples of the substrate (substrate) are, for example, glass, metal (silicon wafer, etc.), cement board, etc. In particular, the peeling layer obtained from the composition for forming a peeling layer of the present invention has sufficient adhesion to it, preferably glass . In addition, the surface of the substrate may be composed of a single material, or may be composed of two or more materials. As the surface of the substrate composed of two or more materials, a certain area of the surface of the substrate is composed of a certain material, and the rest of the surface is composed of other materials, and a certain material on the entire surface of the substrate has a pattern of dots, lines and intervals. Patterns and other patterns exist in other materials.

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 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 is adjusted to achieve the desired thickness.

The peeling layer of the present invention has excellent adhesion to the substrate, especially to the glass substrate, and has moderate adhesion and moderate peelability 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, because the resin substrate can be peeled from the substrate together with the circuit formed on the resin substrate. Use it more appropriately.

[Method of manufacturing 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 release layer for slit coating of the present invention, a release layer is formed on a glass substrate by the aforementioned method. The resin substrate forming solution for forming a resin substrate is coated on the release layer, and the resulting coating film is fired to form a resin substrate fixed to the glass substrate via the release layer of the present invention.

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

The resin substrate is formed so that the entire surface of the release layer is covered by the resin substrate with a larger area than the area of the release layer. Examples of the resin substrate include a resin substrate made of acrylic polymer or a resin substrate made of cycloolefin polymer. The method of forming the resin substrate only needs to follow a common method. Furthermore, as the aforementioned resin substrate, a light transmittance with a wavelength of 400 nm of 80% or more is preferable.

Secondly, the peeling layer of the present invention is fixed to the resin substrate of the base body, and the desired circuit is formed as required. Then, for example, the resin substrate is cut along the peeling layer, and the resin substrate and the circuit are peeled from the peeling layer to remove the resin substrate. Separated from the substrate. At this time, a part of the base body can also be cut together with the release layer. If the peeling layer of the present invention is used, the resin substrate can be peeled from the peeling layer with a peeling force of 0.15N/25mm or less, especially 0.1N/25mm or less. [Example]

Hereinafter, synthesis examples, preparation examples, examples, and comparative examples are given to explain the present invention in more detail, but the present invention is not limited to the following examples.

The compounds used in the following examples are as follows. In addition, the vapor pressure is a value at 20°C. PGME: Propylene glycol monomethyl ether (vapor pressure 1200Pa) PGMEA: Propylene glycol monomethyl ether acetate (vapor pressure 500Pa) EL: ethyl lactate (vapor pressure 279Pa) GBL: γ-butyrolactone (vapor pressure 150Pa) DEGEEA: Diethylene glycol monoethyl ether acetate (vapor pressure 6Pa) Triglyme: Triethylene glycol dimethyl ether (vapor pressure 120Pa) Diglyme: Diethylene glycol dimethyl ether (vapor pressure 330Pa) PL-LI: 1,3,4,6-Tetra (methoxyethyl) glycoluril (manufactured by ALLNEX, 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-hexafluoropropyl 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).

[1] Synthesis of polymers [Synthesis example 1] Synthesis of polyurea (L1) Dissolve 100 g of monoallyl diglycidyl isocyanuric acid (manufactured by Shikoku Chemical Industry Co., Ltd.), 66.4 g of 5,5-diethylbarbituric acid and 4.1 g of benzyltriethylammonium chloride in After 682 g of PGME, it was reacted at 130° C. for 24 hours to obtain a solution containing polyurea (L1) (solid content concentration 20% by mass). As a result of GPC analysis, the obtained polyurea (L1) had an Mw of 8,000 and a Mw/Mn of 1.5.

[Synthesis example 2] Synthesis of acrylic polymer (S1) 4.02 g of HFiPMA, 2.22 g of HPMA, 5.00 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 obtain an acrylic polymer (S1) solution (solid content concentration 20% by mass). 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 3] Synthesis of acrylic polymer (S2) HFiPMA3.98g, HPMA2.43g, IBXA5.00g, and AIBN 0.46g were dissolved in PGME49.8g 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:HPMA:IBXA=30:30:40. As a result of GPC analysis, the obtained acrylic polymer (S2) had Mw of 4,720 and Mw/Mn of 1.7.

[2] Preparation of composition for resin substrate formation [Preparation example 1] Preparation of composition F1 for forming a resin substrate Into a pear-shaped flask filled with 100 g of carbon tetrachloride, add 10 g of ZEONOR (registered trademark) 1020R (cycloolefin polymer made by ZEON (Stock) in Japan) and 3 g of EPOLEAD (registered trademark) GT401 (made by DAICEL (Stock)) . This solution was stirred in a nitrogen atmosphere for 24 hours to dissolve, and a composition F1 for forming a resin substrate was prepared.

[3] Preparation of composition for forming release layer for slit coating [Example 1-1] Preparation of composition 1 for forming peeling layer To 20 g of the reaction solution obtained in Synthesis Example 1, 1.00 g of PL-LI, 0.12 g of PPTS, 1.50 g of acrylic polymer (S1) solution and PGMEA were added, and diluted with PGME to a solid content concentration of 5 mass%, and a PGMEA concentration of 30 Mass %, the composition 1 for peeling layer formation was prepared.

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

[Example 1-3] Preparation of composition 3 for forming peeling layer Except that EL was used instead of PGMEA, and the solid content concentration was set to 5 mass% and the EL concentration was set to 30 mass %, the release layer forming composition 3 was prepared in the same manner as in Example 1-1.

[Example 1-4] Preparation of composition 4 for forming peeling layer Except that EL was used instead of PGMEA, the solid content concentration was 5 mass %, and the EL concentration was 70 mass %, the composition 4 for peeling layer formation was prepared in the same manner as in Example 1-1.

[Example 1-5] Preparation of composition 5 for forming peeling layer Except that GBL was used instead of PGMEA, the solid content concentration was 5 mass %, and the GBL concentration was 30 mass %, the composition 5 for peeling layer formation was prepared by the same method as Example 1-1.

[Example 1-6] Preparation of composition 6 for forming peeling layer Except that GBL was used instead of PGMEA, the solid content concentration was set to 5 mass%, and the GBL concentration was set to 10 mass%, a peeling layer forming composition 6 was prepared in the same manner as in Example 1-1.

[Example 1-7] Preparation of composition 7 for forming peeling layer Except that Triglyme was used instead of PGMEA, and the solid content concentration was set to 5% by mass and the Triglyme concentration was set to 30% by mass, the release layer forming composition 5 was prepared in the same manner as in Example 1-1.

[Example 1-8] Preparation of composition 8 for forming peeling layer Except that Triglyme was used instead of PGMEA, and the solid content concentration was 5 mass %, and the Triglyme concentration was 10 mass %, the composition 8 for peeling layer formation was prepared in the same manner as in Example 1-1.

[Example 1-9] Preparation of composition 9 for forming peeling layer Except that Diglyme was used instead of PGMEA, and the solid content concentration was set to 5 mass%, and the Diglyme concentration was set to 10 mass%, a release layer forming composition 9 was prepared in the same manner as in Example 1-1.

[Example 1-10] Preparation of composition 10 for forming peeling layer Except that DEGEEA was used instead of PGMEA, and the solid content concentration was set to 5% by mass and the DEGEEA concentration was set to 30% by mass, the release layer forming composition 10 was prepared in the same manner as in Example 1-1.

[Example 1-11] Preparation of composition 11 for forming peeling layer To 20 g of the reaction solution obtained in Synthesis Example 1, add 1.28 g of PL-LI, 0.12 g of PPTS, 6.00 g of acrylic polymer (S1) solution and PGMEA, and dilute with PGME to a solid content concentration of 5 mass% and a PGMEA concentration of 30 Mass %, the composition 11 for peeling layer formation was prepared.

[Example 1-12] Preparation of composition 12 for forming peeling layer To 20 g of the reaction solution obtained in Synthesis Example 1, 1.00 g of PL-LI, 0.12 g of PPTS, 1.50 g of acrylic polymer (S2) solution and PGMEA were added, and diluted with PGME to a solid content concentration of 5 mass%, and a PGMEA concentration of 30 Mass %, the composition 12 for peeling layer formation was prepared.

[Example 1-13] Preparation of composition 13 for forming peeling layer To 20 g of the reaction solution obtained in Synthesis Example 1, 1.00 g of PL-LI, 0.60 g of PPTS, 1.50 g of acrylic polymer (S2) solution and GBL were added, and diluted with PGME to a solid content concentration of 5 mass% and a GBL concentration of 30 Mass %, the composition 13 for peeling layer formation was prepared.

[Example 1-14] Preparation of composition 14 for forming peeling layer To 20 g of the reaction solution obtained in Synthesis Example 1, 1.00 g of PL-LI, 0.60 g of PPTS, 1.50 g of acrylic polymer (S1) solution and PGMEA were added, and diluted with PGME to a solid content concentration of 5 mass%, and a PGMEA concentration of 30 Mass %, the composition 14 for peeling layer formation was prepared.

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

[Comparative example 1] Preparation of composition 16 for forming peeling layer Except that PGME was used instead of PGMEA, and the solid content concentration was set to 5 mass %, and the PGME concentration was set to 95 mass %, the peeling layer forming composition 16 was prepared in the same manner as in Example 1-1.

[4] Production and evaluation of peeling layer [Example 2-1] The composition 1 for forming a peeling layer was coated on the glass using a slit coater (manufactured by Techno Machine (stock), product name: desktop type, conditions: liquid volume 7μL, gap 25μm, coating speed 20mm/sec) On the substrate (100mm×100mm, the same below). Subsequently, the obtained coating film reached a pressure reduction degree in 5 seconds with a vacuum dryer (degree of pressure reduction 60 Pa), and was vacuum dried. Next, use a hot plate to heat at 100°C for 2 minutes, and then use a hot plate to heat at 230°C for 10 minutes to form a peeling layer with a thickness of about 0.1 μm on the glass substrate to obtain a glass substrate 1 with a peeling layer.

[Example 2-2] Except having used the composition 2 for peeling layer formation instead of the composition 1 for peeling layer formation, it carried out similarly to Example 2-1, and obtained the glass substrate 2 with a peeling layer.

[Example 2-3] Except having used the composition 3 for peeling layer formation instead of the composition 1 for peeling layer formation, it carried out similarly to Example 2-1, and obtained the glass substrate 3 with a peeling layer.

[Example 2-4] Except having used the composition 4 for peeling layer formation instead of the composition 1 for peeling layer formation, it carried out similarly to Example 2-1, and obtained the glass substrate 4 with a peeling layer.

[Example 2-5] Except having used the composition 5 for peeling layer formation instead of the composition 1 for peeling layer formation, it carried out similarly to Example 2-1, and obtained the glass substrate 5 with a peeling layer.

[Example 2-6] Except having used the composition 6 for peeling layer formation instead of the composition 1 for peeling layer formation, it carried out similarly to Example 2-1, and obtained the glass substrate 6 with a peeling layer.

[Example 2-7] The glass substrate 7 with a peeling layer was obtained by the same method as Example 2-1 except having used the composition 7 for peeling layer formation instead of the composition 1 for peeling layer formation.

[Example 2-8] Except having used the composition 8 for peeling layer formation instead of the composition 1 for peeling layer formation, it carried out similarly to Example 2-1, and obtained the glass substrate 8 with a peeling layer.

[Example 2-9] The glass substrate 9 with a peeling layer was obtained by the same method as Example 2-1 except having used the composition 9 for peeling layer formation instead of the composition 1 for peeling layer formation.

[Example 2-10] Except having used the composition 10 for peeling layer formation instead of the composition 1 for peeling layer formation, the glass substrate 10 with a peeling layer was obtained by the same method as Example 2-1.

[Example 2-11] The glass substrate 11 with a peeling layer was obtained by the same method as Example 2-1 except using the composition 11 for peeling layer formation instead of the composition 1 for peeling layer formation.

[Example 2-12] The glass substrate 12 with a peeling layer was obtained by the same method as Example 2-1 except having used the composition 12 for peeling layer formation instead of the composition 1 for peeling layer formation.

[Example 2-13] Except having used the composition 13 for peeling layer formation instead of the composition 1 for peeling layer formation, it carried out similarly to Example 2-1, and obtained the glass substrate 13 with a peeling layer.

[Example 2-14] The glass substrate 14 with a peeling layer was obtained by the same method as Example 2-1 except using the composition 14 for peeling layer formation instead of the composition 1 for peeling layer formation.

[Example 2-15] The glass substrate 15 with a peeling layer was obtained by the same method as Example 2-1 except having used the composition 15 for peeling layer formation instead of the composition 1 for peeling layer formation.

[Comparative Example 2-1] The glass substrate 16 with a peeling layer was obtained by the same method as Example 2-1 except having used the composition 16 for peeling layer formation instead of the composition 1 for peeling layer formation. As a result of confirming the unevenness of the peeling layer with Na lamp, the peeling layer was cloudy, and it was confirmed that there were many unevenness.

[5] Production of resin substrate [Example 3-1] On the glass substrate 1 with a peeling layer, using a spin coater (condition: rotation speed 200 rpm for about 15 seconds), the resin substrate forming composition F1 was applied to the peeling layer (resin film) on the glass substrate. The resulting coating film was heated at 80°C for 2 minutes using a hot plate, and then heated at 230°C for 30 minutes using a hot plate to form a resin substrate with a thickness of about 3 μm on the peeling layer to obtain a glass substrate 1 with resin substrate/peeling layer. Subsequently, using an ultraviolet-visible spectrophotometer (Shimadzu Corporation UV-2600) to measure the light transmittance, the resin substrate showed a transmittance of more than 90% at 400nm.

[Example 3-2] Except having used the glass substrate 2 with a peeling layer instead of the glass substrate 1 with a peeling layer, the glass substrate 2 with a resin substrate/peeling layer was obtained by the same method as Example 3-1. The resin substrate shows a transmittance of over 90% at 400nm.

[Example 3-3] Except having used the glass substrate 3 with a peeling layer instead of the glass substrate 1 with a peeling layer, the glass substrate 3 with a resin substrate/peeling layer was obtained by the same method as Example 3-1. The resin substrate shows a transmittance of over 90% at 400nm.

[Example 3-4] Except having used the glass substrate 4 with a peeling layer instead of the glass substrate 1 with a peeling layer, the glass substrate 4 with a resin substrate/peeling layer was obtained by the same method as Example 3-1. The resin substrate shows a transmittance of over 90% at 400nm.

[Example 3-5] Except having used the glass substrate 5 with a peeling layer instead of the glass substrate 1 with a peeling layer, the glass substrate 5 with a resin substrate/peeling layer was obtained by the same method as Example 3-1. The resin substrate shows a transmittance of over 90% at 400nm.

[Example 3-6] Except having used the glass substrate 6 with a peeling layer instead of the glass substrate 1 with a peeling layer, the glass substrate 6 with a resin substrate/peeling layer was obtained by the same method as Example 3-1. The resin substrate shows a transmittance of over 90% at 400nm.

[Example 3-7] Except having used the glass substrate 7 with a peeling layer instead of the glass substrate 1 with a peeling layer, the glass substrate 7 with a resin substrate/peeling layer was obtained by the same method as Example 3-1. The resin substrate shows a transmittance of over 90% at 400nm.

[Example 3-8] Except having used the glass substrate 8 with a peeling layer instead of the glass substrate 1 with a peeling layer, the glass substrate 8 with a resin substrate/peeling layer was obtained by the same method as Example 3-1. The resin substrate shows a transmittance of over 90% at 400nm.

[Example 3-9] Except having used the glass substrate 9 with a peeling layer instead of the glass substrate 1 with a peeling layer, the glass substrate 9 with a resin substrate/peeling layer was obtained by the same method as Example 3-1. The resin substrate shows a transmittance of over 90% at 400nm.

[Example 3-10] Except having used the glass substrate 10 with a peeling layer instead of the glass substrate 1 with a peeling layer, the glass substrate 10 with a resin substrate/peeling layer was obtained by the same method as Example 3-1. The resin substrate shows a transmittance of over 90% at 400nm.

[Example 3-11] Except having used the glass substrate 11 with a peeling layer instead of the glass substrate 1 with a peeling layer, the glass substrate 11 with a resin substrate/peeling layer was obtained by the same method as Example 3-1. The resin substrate shows a transmittance of over 90% at 400nm.

[Example 3-12] Except having used the glass substrate 12 with a peeling layer instead of the glass substrate 1 with a peeling layer, the glass substrate 12 with a resin substrate/peeling layer was obtained by the same method as Example 3-1. The resin substrate shows a transmittance of over 90% at 400nm.

[Example 3-13] Except having used the glass substrate 13 with a peeling layer instead of the glass substrate 1 with a peeling layer, the glass substrate 13 with a resin substrate/peeling layer was obtained by the same method as Example 3-1. The resin substrate shows a transmittance of over 90% at 400nm.

[Example 3-14] Except for using the glass substrate 14 with a peeling layer instead of the glass substrate 1 with a peeling layer, the glass substrate 14 with a resin substrate/peeling layer was obtained by the same method as Example 3-1. The resin substrate shows a transmittance of over 90% at 400nm.

[Example 3-15] Except having used the glass substrate 15 with a peeling layer instead of the glass substrate 1 with a peeling layer, the glass substrate 15 with a resin substrate/peeling layer was obtained by the same method as Example 3-1. The resin substrate shows a transmittance of over 90% at 400nm.

[6] Evaluation of peelability For glass substrates 1 to 16 with a peeling layer, confirm the adhesion between the peeling layer and the glass substrate by the following method. For glass substrates 1 to 15 with a resin substrate/peeling layer without uneven peeling layer, confirm the peeling layer and The peelability of the resin film. In addition, the following tests were performed on the same glass substrate.

(1) Evaluation of adhesion between peeling layer and glass substrate The peeling layer on the glass substrates 1-16 with peeling layer is cross-cut (2mm in vertical and horizontal, the same below), and 25 grids are cut. That is, by the cross cutting, 25 blocks of 2mm square are formed. The adhesive tape was attached to the 25 cut part, the tape was peeled off, and the adhesion was evaluated based on the following criteria. The results are shown in Table 1. <Judgment criteria> 5B: 0% peeling (not peeling) 4B: Less than 5% peel 3B: 5% to less than 15% peeling 2B: 15% ~ less than 35% peeling 1B: 35% ~ less than 65% peeling 0B: 65% ~ 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 Make short strips of 25mm×50mm on glass substrates 1-15 with resin substrate/peeling layer. Furthermore, after attaching CELLOTAPE (registered trademark) (CT-24 manufactured by NICHIBON Co., Ltd.), using Autograph AGS-500N (manufactured by Shimadzu Corporation), peeled at a peeling angle of 90° and a peeling speed of 300 mm/min, and the peeling was measured. force. Also, those that could not be peeled off were recorded as not peelable. The results are shown in Table 1.

From the results shown in Table 1, the peeling layer of the example has excellent adhesion to the glass substrate and excellent peelability with the resin substrate. On the other hand, the surface of the peeling layer of the comparative example was mostly uneven and became cloudy.

From the above results, it is shown that if the composition for forming a release layer for slit coating of the present invention is used, even if it is coated by the slit coating method, coating unevenness does not occur, and it is possible to obtain A release layer with excellent adhesion, moderate adhesion to the resin substrate, and moderate releasability.

Claims (11)

A composition for forming a release layer for slit coating, comprising (A) a polyurea containing a repeating unit represented by the following formula (1), (B) an acid compound or a salt thereof, and (C) selected from those having a hydroxyl group The crosslinking agent of an alkyl group and/or a nitrogen atom substituted by an alkoxymethyl group, (D) contains a repeating unit represented by the following formula (a1), a repeating unit represented by the following formula (b), and the following The polymer additive of the repeating unit represented by formula (c), and (E) a solvent containing at least one solvent with a vapor pressure of 800 Pa or less at 20°C, (D) the polymer additive relative to (A) 100 mass of polyurea Parts, containing 3~100 parts by mass,

[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 a carbon number of 1 to 6, an alkenyl group with a carbon number of 3 to 6, a benzyl group or a phenyl group. At least one of the group consisting of 6 alkyl groups, halogen atoms, C1-C6 alkoxy groups, nitro groups, cyano groups, hydroxyl groups and C1-C6 alkylthio groups, and R ¹ And R ² can also be bonded to each other together with the bonded carbon atoms to form a carbon 3-6 ring, R ³ is an alkyl with 1 to 6 carbons, an alkenyl with 3 to 6 carbons, and a benzyl group Or phenyl group, the aforementioned phenyl group can be selected from alkyl groups having 1 to 6 carbon atoms, halogen atoms, alkoxy groups having 1 to 6 carbon atoms, nitro groups, cyano groups, hydroxyl groups and alkylthio groups having 1 to 6 carbon atoms At least one group in the group 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, phenylene, or naphthalene with 1 to 10 carbon atoms The aforementioned phenylene, naphthylene and anthracene groups can be selected from alkyl groups with 1 to 6 carbons, halogen atoms, alkoxy groups with 1 to 6 carbons, nitro, cyano, Substitution of at least one group of hydroxyl group and alkylthio group with carbon number 1~6, n ¹ and n ² are independently 0 or 1)]

(In the formula, R ^{A is} independently a hydrogen atom or a methyl group, R ^B1 is a branched alkyl group with 3 or 4 carbons in which at least one hydrogen atom is replaced by a fluorine atom, and R ^C is a hydroxyalkane with 1 to 10 carbons. R ^D is a polycyclic alkyl group with 6 to 20 carbons or an aryl group with 6 to 12 carbons). For example, the composition for forming a release layer for slit coating according to claim 1, wherein in the repeating unit represented by formula (b) of (D) polymer additive, R ^C is a hydroxyalkyl group with 2 to 10 carbon atoms, The carbon atom to which the hydroxyl 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 in all the repeating units of the polymer additive (D). The composition for forming a release layer for slit coating according to claim 1 or 2, wherein X ¹ is a base represented by formula (1-3). The composition for forming a release layer for slit coating according to claim 3, wherein R ³ is a 2-propenyl group. The composition for forming a release layer for slit coating according to any one of claims 1 to 4, wherein Q ¹ is a base represented by formula (1-5). The composition for forming a release layer for slit coating 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 slit coating according to any one of claims 1 to 6, wherein (C) the crosslinking agent is any one of the following formulas (C-1) to (C-7) Represents the compound,

(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). The composition for forming a release layer for slit coating according to any one of claims 1 to 7, wherein the content of (C) crosslinking agent is 10-100 mass parts relative to 100 mass parts of (A) polyurea Copies. A peeling layer obtained from the composition for forming a peeling layer for slit coating according to any one of claims 1 to 8. A laminate formed by laminating a resin layer with a light transmittance of 80% or more at a wavelength of 400 nm on a release layer as in claim 9. A method for manufacturing a resin substrate, which comprises The step of applying the composition for forming a release layer for slit coating according to any one of claims 1 to 8 on a substrate to form a release 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 0.15N/25mm or less.