TW202311312A - Composition for forming release layer, and release layer - Google Patents

Abstract

Provided is a composition for forming a release layer comprising a polymer including a repeating unit having a photosensitive group that undergoes photo-Fries rearrangement.

Description

Composition for forming release layer and release layer

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

In recent years, in addition to the characteristics of thinning and lightening, electronic devices are also required to be endowed with a bendable function. Therefore, it is required to replace the heavy, fragile and inflexible glass substrates with lightweight flexible plastic substrates.

In particular, as a new-generation display, it is required to develop an active matrix full-color TFT display panel using a lightweight flexible plastic substrate (hereinafter also referred to as a resin substrate). In addition, for touch panel displays, materials corresponding to flexibility such as transparent electrodes and resin substrates of touch panels used in combination with display panels have been developed. As a transparent electrode, other transparent electrode materials such as transparent conductive polymers such as PEDOT, metal nanowires, and their hybrid systems have been proposed from the conventionally used ITO (Patent Documents 1 to 4).

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

In general, for stable production of flexible touch screen panels, a peeling (adhesive) layer is formed on a support substrate such as a glass substrate, and a device composed of a resin substrate or the like is fabricated on it. The above-mentioned adhesive layer was peeled off and the device was produced (Patent Document 8). A device composed of a resin substrate or the like produced on the peeling layer cannot be peeled from the support substrate during the process, but a low peeling force is required for peeling. In particular, in the case of peeling from the support substrate in the production process, there is a possibility that the yield will be greatly reduced. [Prior Art Literature] [Patent Document]

[Patent Document 1] International Publication No. 2012/147235 [Patent Document 2] Japanese Unexamined Patent Publication No. 2009-283410 [Patent Document 3] Japanese National Publication No. 2010-507199 [Patent Document 4] Japanese Patent Laid-Open No. 2009-205924 [Patent Document 5] International Publication No. 2017/002664 [Patent Document 6] International Publication No. 2016/160338 [Patent Document 7] Japanese Patent Laid-Open No. 2015-166145 [Patent Document 8] Japanese Patent Laid-Open No. 2016-531358

[Problem to be Solved by the Invention]

The present invention has been made in view of the foregoing circumstances, and an object of the present invention is to provide a composition for forming a peeling layer that can impart a peeling layer that has high heat resistance and good peelability and can suppress unnecessary peeling in steps. [Means to solve the problem]

In order to achieve the aforementioned object, the present inventors, as a result of repeated careful studies, have found that a peeling layer obtained from a composition for forming a peeling layer comprising a polymer containing a photosensitive group capable of causing photo-Friesian rearrangement The repeating unit has good detachability with the resin substrate produced on the release layer, and the adhesion with the resin substrate can be improved only in the designated area by exposure, and the present invention has been completed.

(式中，Ar ¹為苯基、1-萘基、2-萘基、2-聯苯基、3-聯苯基或4-聯苯基，該等基之氫原子之一部分或全部可被碳數1~6之烷基、碳數1~6之烷氧基、氯原子或溴原子所取代，但式中之氧原子之鄰位及對位之至少一者為氫原子； Ar ²為1,2-伸苯基、1,3-伸苯基、1,4-伸苯基、1,2-伸萘基、1,3-伸萘基、1,4-伸萘基、1,5-伸萘基、1,6-伸萘基、1,7-伸萘基、1,8-伸萘基、2,3-伸萘基、2,6-伸萘基、2,2’-亞聯苯基(biphenylylene)、2,3’-亞聯苯基、2,4’-亞聯苯基、3,3’-亞聯苯基、3,4’-亞聯苯基或4,4’-亞聯苯基，該等基之氫原子之一部分或全部可被碳數1~6之烷基、碳數1~6之烷氧基、氯原子或溴原子所取代，式中之氧原子之鄰位及對位之至少一者為氫原子， R ¹為碳數1~6之烷基或苯基； X ¹及X ²係各自獨立為單鍵或碳數1~20之伸烷基，該伸烷基之1個或複數個-CH ₂-可被選自-O-、-C(=O)-O-及-O-C(=O)-之至少1個基所取代； A ¹及A ²係各自獨立為包含碳-碳雙鍵之自由基聚合性基。) 3.如2之剝離層形成用樹脂組成物，其中前述自由基聚合性基為下述式(A-1)~(A-4)之任一式所示者。

(R ^A係各自獨立為氫原子或甲基。) 4.如1或2之剝離層形成用樹脂組成物，其中(A)聚合物為更包含源自下述式(b)所示單體之重複單位及源自下述式(c)所示單體之重複單位的聚合物。

(式中，R ^A係各自獨立為氫原子或甲基； R ^B為至少1個氫原子被氟原子取代之碳數3或4之分枝狀之烷基； R ^C為碳數2~10之羥基烷基。) 5.如1~4中任一項之剝離層形成用組成物，其中更包含(B)具有羥基或羧基之樹脂。 6.如1~5中任一項之剝離層形成用組成物，其中(B)具有羥基或羧基之樹脂為具有羥基之聚脲、具有羥基或羧基之丙烯酸聚合物、具有羥基之聚酯，或具有羥基烷基之纖維素或其衍生物。 7.如1~6中任一項之剝離層形成用組成物，其中更包含(C)交聯劑，該(C)交聯劑為選自具有羥基烷基及/或被烷氧基甲基取代之氮原子之化合物。 8.如1~7中任一項之剝離層形成用組成物，其中更包含(D)交聯觸媒。 9.一種剝離層，其係由如1~8中任一項之剝離層形成用組成物所得者。 10.一種積層體，其係在如9之剝離層上積層有樹脂層者，該樹脂層在波長400nm之光穿透率為80%以上。 11.如10之積層體，其中前述樹脂基板為包含環氧化合物之熱硬化膜。 12.一種剝離層之形成方法，其包含：使用如1~8中任一項之剝離層形成用組成物在基體上形成樹脂膜的步驟，及，使用紫外線來曝光前述樹脂膜之指定區域的步驟。 13.一種樹脂基板之製造方法，其包含：使用如1~8中任一項之剝離層形成用組成物在基體上形成樹脂膜的步驟、使用紫外線來曝光前述樹脂膜之指定區域的步驟、在前述剝離層上形成波長400nm之光穿透率為80%以上之樹脂基板的步驟，及，使用1.0N/25mm以下之剝離力來將形成於前述剝離層上之樹脂基板予以剝離的步驟。 [發明效果] That is, the present invention provides the following release layer-forming composition and release layer. 1. A composition for forming a release layer, comprising (A) a polymer comprising a repeating unit having a photosensitive group that causes photo-Fries rearrangement. 2. The composition for forming a release layer according to 1, wherein the repeating unit having a photosensitive group that causes photo-Fries rearrangement is derived from a monomer represented by the following formula (a1) or (a2).

(wherein, Ar is ^phenyl , 1-naphthyl, 2-naphthyl, 2-biphenyl, 3-biphenyl or 4-biphenyl, and a part or all of the hydrogen atoms of these groups can be replaced by Alkyl with 1~6 carbons, alkoxyl with 1~6 carbons, chlorine atom or bromine atom, but at least one of the ortho and para positions of the oxygen atom in the formula is a hydrogen atom; Ar ² is 1,2-phenylene, 1,3-phenylene, 1,4-phenylene, 1,2-naphthyl, 1,3-naphthyl, 1,4-naphthyl, 1, 5-Naphthyl, 1,6-Naphthyl, 1,7-Naphthyl, 1,8-Naphthyl, 2,3-Naphthyl, 2,6-Naphthyl, 2,2' -biphenylene, 2,3'-biphenylene, 2,4'-biphenylene, 3,3'-biphenylene, 3,4'-biphenylene or 4 , 4'-biphenylene, a part or all of the hydrogen atoms of these groups may be replaced by an alkyl group with 1 to 6 carbons, an alkoxy group with 1 to 6 carbons, a chlorine atom or a bromine atom, where At least one of the ortho and para positions of the oxygen atom is a hydrogen atom, R ¹ is an alkyl or phenyl group with 1 to 6 carbons; X ¹ and X ² are each independently a single bond or a carbon number of 1 to 20 Alkylene group, one or more -CH ₂ - of the alkylene group may be substituted by at least one group selected from -O-, -C(=O)-O- and -OC(=O)- ; A ¹ and A ² are each independently a free radical polymerizable group comprising a carbon-carbon double bond.) 3. The resin composition for forming a release layer as in 2, wherein the aforementioned free radical polymerizable group is the following formula (A -1)~(A-4) represented by any of the formulas.

( ^RA is each independently a hydrogen atom or a methyl group.) 4. The resin composition for peeling layer formation as in 1 or 2, wherein (A) polymer further comprises a monomer derived from the following formula (b) The repeating unit of and the polymer derived from the repeating unit of the monomer represented by the following formula (c).

(In the formula, R ^A is each independently a hydrogen atom or a methyl group; R ^B is a branched alkyl group with 3 or 4 carbons in which at least one hydrogen atom is replaced by a fluorine atom; R ^C is a branched alkyl group with 2 to 10 carbons 5. The composition for forming a release layer according to any one of 1 to 4, which further includes (B) a resin having a hydroxyl group or a carboxyl group. 6. The composition for forming a release layer according to any one of 1 to 5, wherein (B) the resin having a hydroxyl group or a carboxyl group is a polyurea having a hydroxyl group, an acrylic polymer having a hydroxyl group or a carboxyl group, or a polyester having a hydroxyl group, Or cellulose or derivatives thereof having a hydroxyalkyl group. 7. The composition for forming a release layer according to any one of 1 to 6, which further comprises (C) a crosslinking agent, and the (C) crosslinking agent is selected from Compounds with substituted nitrogen atoms. 8. The composition for forming a release layer according to any one of 1 to 7, further comprising (D) a crosslinking catalyst. 9. A release layer obtained from the composition for forming a release layer according to any one of 1 to 8. 10. A laminate comprising a resin layer laminated on the peeling layer as in 9, and the light transmittance of the resin layer at a wavelength of 400 nm is 80% or more. 11. The laminate according to 10, wherein the resin substrate is a thermosetting film containing an epoxy compound. 12. A method for forming a release layer, comprising: using the composition for forming a release layer according to any one of 1 to 8 to form a resin film on a substrate, and exposing a predetermined area of the resin film with ultraviolet rays step. 13. A method for manufacturing a resin substrate, comprising: using the composition for forming a release layer according to any one of 1 to 8 to form a resin film on a substrate; exposing a predetermined area of the resin film with ultraviolet rays; A step of forming a resin substrate with a light transmittance of 400nm at a wavelength of 80% or more on the release layer, and a step of peeling the resin substrate formed on the release layer with a peeling force of 1.0N/25mm or less. [Invention effect]

By using the composition for forming a release layer of the present invention, it is possible to obtain a release layer with good reproducibility. The release layer has good releasability from a resin substrate produced on the release layer and can be formed only by exposure. The designated area improves the adhesion with the resin substrate. In addition, in the manufacturing process of flexible electronic devices, it will not cause damage to the resin substrate formed on the base, or the circuit installed on it, and can suppress unnecessary peeling in the middle of manufacturing, and change when necessary. It is possible to separate the circuit and the like together with the resin substrate from the base body. Therefore, the composition for forming a release layer of the present invention can contribute to speeding up the manufacturing process of a flexible electronic device including a resin substrate, improving its yield, and the like.

[Composition for peeling layer formation]

The composition for peeling layer formation of this invention contains: (A) The polymer containing the repeating unit which has the photosensitive group which causes photofries rearrangement.

[(A) Polymer] The (A) component in the composition for peeling layer formation of this invention is a polymer containing the repeating unit which has the photosensitive group which causes photofries rearrangement.

Photo-Fries rearrangement is the generation of acylphenols substituted with acyl groups at the ortho and para positions by light irradiation of phenyl esters. Phenyl ester is a general term for esters formed between phenols and acids, and refers to esters with carboxylic acids. This rearrangement reaction is considered to proceed by a free radical mechanism from an excited singlet state.

The peeling layer obtained from the aforementioned polymer undergoes photo-Fries rearrangement by light irradiation to generate acylphenol. Since the generated acyl phenol exhibits hydrophilicity, and the cross-linking reaction with the resin substrate etc. on the release layer can proceed, it becomes possible to control the releasability of the resin substrate etc. on the release layer by light irradiation .

As said monomer, what is represented by following formula (a1) or (a2) is preferable.

In formula (a1) and (a2), Ar ¹ is phenyl, 1-naphthyl, 2-naphthyl, 2-biphenyl, 3-biphenyl or 4-biphenyl, and the hydrogen atom of these bases A part or all of them may be substituted by an alkyl group with 1 to 6 carbons, an alkoxy group with 1 to 6 carbons, a chlorine atom or a bromine atom, but at least one of the ortho and para positions of the oxygen atom in the formula is A hydrogen atom.

In formula (a1) and (a2), Ar ² is 1,2-phenylene, 1,3-phenylene, 1,4-phenylene, 1,2-naphthyl, 1,3-phenylene Naphthyl, 1,4-naphthyl, 1,5-naphthyl, 1,6-naphthyl, 1,7-naphthyl, 1,8-naphthyl, 2,3-naphthyl , 2,6-naphthyl, 2,2'-biphenylene, 2,3'-biphenylene, 2,4'-biphenylene, 3,3'-biphenylene 3,4'-biphenylene or 4,4'-biphenylene, part or all of the hydrogen atoms of these groups can be replaced by an alkyl group with 1 to 6 carbons or an alkane with 1 to 6 carbons Oxygen, chlorine atom or bromine atom, but at least one of the ortho and para positions of the oxygen atom in the formula is a hydrogen atom.

In formulas (a1) and (a2), R ¹ is an alkyl group or phenyl group having 1 to 6 carbon atoms.

In formulas (a1) and (a2), X ¹ and X ² are each independently a single bond or an alkylene group with 1 to 20 carbon atoms, and one or more -CH ₂ - of the alkylene group can be selected from Substituted by at least one of -O-, -C(=O)-O- and -OC(=O)-.

The above-mentioned alkyl group having 1 to 6 carbon atoms may be any of linear, branched and cyclic, and specific examples thereof include methyl, ethyl, n-propyl, isopropyl, Cyclopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, cyclobutyl, n-pentyl, cyclopentyl, n-hexyl, cyclohexyl, etc.

The aforementioned alkoxy group having 1 to 6 carbon atoms may be any of linear, branched, and cyclic, and specific examples thereof include, for example, methoxy, ethoxy, n-propoxy, Isopropoxy, cyclopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, cyclobutoxy, n-pentyloxy, cyclopentyloxy, n -hexyloxy, cyclohexyloxy and the like.

The aforementioned alkylene group having 1 to 20 carbons may be any of linear, branched, and cyclic, and specific examples thereof include, for example, methylene, methylmethylene, dimethylmethylene Methyl, ethylenyl, trimethylene, propylenyl, tetramethylene, pentamethylene, hexamethylene, etc.

Ar ¹ is preferably unsubstituted phenyl, 1-naphthyl, 2-naphthyl, 3-biphenyl, or 4-biphenyl. Ar ² is preferably unsubstituted 1,4-phenylene group or 4,4'-biphenylene group. X ¹ and X ² are preferably single bonds.

(R ^A係各自獨立為氫原子或甲基。) In formulas (a1) and (a2), A ¹ and A ² are each independently a radically polymerizable group containing a carbon-carbon double bond. As the radical polymerizable group, one represented by any one of the following formulas (A-1) to (A-4) is preferable.

(The R ^{A series} are each independently a hydrogen atom or a methyl group.)

A ¹ and A ² are preferably represented by formula (A-1) or (A-2).

Specific examples of the monomer represented by the formula (a1) include those represented by the following formulas (a1-1) to (a1-5), but are not limited thereto. In addition, in the following formulae, ^A1 and ^X1 are the same as above.

Preferable specific examples of the monomer represented by the formula (a1) include those represented by the following formulas (a1-1') to (a1-5'), but are not limited thereto.

Specific examples of the monomer represented by the formula (a2) include those represented by the following formulas (a2-1) to (a2-4), but are not limited thereto. In addition, in the following formula, A ² and X ² are the same as above.

Preferable specific examples of the monomer represented by the formula (a2) include those represented by the following formulas (a2-1') to (a2-4'), but are not limited thereto.

In the polymer of the component (A), the content rate of the repeating unit derived from the monomer represented by the formula (a1) and/or (a2) may be 100 mole % in the total repeating unit, and it is 10~60 mole % is better, preferably 15-50 mole %.

The polymer of the component (A) preferably further includes a repeating unit derived from a monomer represented by the following formula (b) and a repeating unit derived from a monomer represented by the following formula (c).

In formulas (b) and (c), R ^A is each independently a hydrogen atom or a methyl group. ^RB is a branched alkyl group having 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 carbon atoms.

Examples of the branched alkyl group having 3 or 4 carbon atoms include isopropyl, isobutyl, sec-butyl and tert-butyl. As R ^B , at least one hydrogen atom of the branched alkyl group is preferably replaced 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 aforementioned hydroxyalkyl group having 2 to 10 carbon atoms include 1-hydroxyethyl, 1-hydroxypropyl, 2-hydroxypropyl, 2-hydroxybutyl, 2-hydroxyhexyl, 2-hydroxyoctyl radical, 2-hydroxydecyl, 1-hydroxy-1-methylethyl, 2-hydroxy-2-methylpropyl, etc.

Examples of the monomer represented by the formula (b) include those represented by the following formulas (b-1) to (b-3), but are not limited thereto. In addition, in the following formulae, R ^A is the same as above.

Examples of the monomer represented by the formula (c) include those represented by the following formulas (c-1) to (c-4), but are not limited thereto. In addition, in the following formulae, R ^A is the same as above.

When the polymer of component (A) contains a repeating unit derived from a monomer represented by formula (b) and a repeating unit derived from a monomer represented by the following formula (c), it is derived from a monomer represented by (b) The content of the repeating unit in the total repeating unit is preferably 5-60 mol%, more preferably 10-50 mol%. The content of the repeating unit derived from the monomer represented by formula (c) is preferably 5-60 mol%, more preferably 10-50 mol%, in the total repeating unit.

(A) The polymer of the component may contain repeating units derived from monomers (hereinafter also referred to as other monomers) other than the aforementioned monomers unless the effect of the present invention is impaired. Examples of other monomers include acrylate compounds, methacrylate compounds, maleimide compounds, acrylamide compounds, acrylonitrile, maleic anhydride, styrene compounds, vinyl compounds and the like.

Specific examples of the aforementioned acrylate compounds include methyl acrylate, ethyl acrylate, isopropyl acrylate, benzyl acrylate, naphthyl acrylate, anthracenyl acrylate, anthracenylmethyl acrylate, Phenyl acrylate, 2,2,2-trifluoroethyl acrylate, tert-butyl acrylate, cyclohexyl acrylate, isobornyl acrylate, 2-methoxyethyl acrylate, methoxy acrylate Triethylene glycol ester, 2-ethoxyethyl acrylate, tetrahydrofurfuryl acrylate, 3-methoxybutyl acrylate, 2-methyl-2-adamantyl acrylate, 2-propane Base-2-adamantyl ester, 8-methyl-8-tricyclo[5.2.1.0(2,6)]decyl acrylate, 8-ethyl-8-tricyclo[5.2.1.0(2, 6)] decyl ester, etc.

Specific examples of the aforementioned methacrylate compounds include, for example, methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, benzyl methacrylate, naphthyl methacrylate, Anthracenyl methacrylate, anthracenylmethyl methacrylate, phenyl methacrylate, 2,2,2-trifluoroethyl methacrylate, tert-butyl methacrylate, methacrylic acid Cyclohexyl ester, Isocamyl methacrylate, 2-Methoxyethyl methacrylate, Methoxytriethylene glycol methacrylate, 2-Ethoxyethyl methacrylate, Methyl Tetrahydrofurfuryl acrylate, 3-methoxybutyl methacrylate, 2-methyl-2-adamantyl methacrylate, 2-propyl-2-adamantyl methacrylate, methyl 8-methyl-8-tricyclo[5.2.1.0(2,6)]decyl methacrylate, 8-ethyl-8-tricyclo[5.2.1.0(2,6)]decyl methacrylate wait.

Specific examples of the aforementioned vinyl compound include vinyl ether, methyl vinyl ether, benzyl vinyl ether, 2-hydroxyethyl vinyl ether, phenyl vinyl ether, and propyl vinyl ether. wait.

Specific examples of the aforementioned styrene compound include styrene, 4-methylstyrene, 4-chlorostyrene, 4-bromostyrene and the like.

Specific examples of the aforementioned maleimide compound include, for example, maleimide, N-methylmaleimide, N-phenylmaleimide, N-cyclohexylmaleimide imine etc.

The weight average molecular weight (Mw) of the polymer of component (A) is preferably 1,000-20,000, more preferably 2,000-10,000. Also, the degree of dispersion (Mw/Mn) is preferably 1.0~3.0, more preferably 1.0~2.5. Also, Mw is a polystyrene conversion measurement value obtained by gel permeation chromatography (GPC).

The method for synthesizing the aforementioned polymer is not particularly limited, and examples thereof include a method of performing a polymerization reaction at a temperature of 50 to 110° C. in a solvent in which the aforementioned monomers and polymerization initiators coexist. At this time, the solvent to be used is not particularly limited as long as it dissolves the aforementioned monomer, polymerization initiator, and the like. As a specific example, what was illustrated as the solvent of (E) component mentioned later is mentioned, for example.

The polymer obtained by this operation is usually in a solution state dissolved in a solvent, and the solution as the (A) component can be used as it is in the present invention.

In addition, the solution of the above-mentioned polymer can be put into hexane, methanol, water, etc. to make reprecipitation, and the obtained precipitate can be separated by filtration, and after washing, it can be carried out by normal temperature or heating under normal pressure or reduced pressure. Dry to recover polymer powder. By this operation, the polymerization initiator or unreacted monomer coexisting with the polymer can be removed, and as a result, a purified polymer powder can be obtained. When the purification cannot be sufficiently performed by one operation, the above-mentioned operation may be repeated by redissolving the obtained powder in a solvent. The powder system of the above-mentioned polymer can be used as (A) component as it is, or it can be used as a solution state by redissolving this powder in the solvent mentioned later, for example.

In the composition for forming a release layer of the present invention, the polymers of the (A) component may be used alone or in combination of two or more.

[(B) Resins with hydroxyl or carboxyl groups] The composition for peeling layer formation of this invention may contain the resin which has a hydroxyl group or a carboxyl group as (B) component as needed. Such a resin is not particularly limited, but polyurea having a hydroxyl group, acrylic polymer having a hydroxyl group or carboxyl group, polyester having a hydroxyl group, or cellulose or derivatives thereof having a hydroxyl group are preferable.

As the aforementioned polyurea having a hydroxyl group, one containing a repeating unit represented by the following formula (1) is preferable.

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 peelability and productivity, A ¹ to A ⁶ are preferably hydrogen atoms.

(式中，*為與式中之羰基之鍵結處。**為與式中之氮原子之鍵結處。) In formula (1), ^X1 is a group represented by the following formula (X1), (X2), (X3) or (X4).

(In the formula, * is the bond with the carbonyl group in the formula. ** is the bond with the nitrogen atom in the formula.)

In the formulas (X1) and (X2), R ¹ and R ² are each independently a hydrogen atom, an alkyl group having 1 to 6 carbons, an alkenyl group having 3 to 6 carbons, benzyl or phenyl. The aforementioned phenyl groups can be selected from the groups 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 Substituted by at least one group. In addition, R ¹ and R ² may also combine with each other to form a ring having 3 to 6 carbon atoms together with the carbon atoms to which they are bonded.

In formula (X3), R ³ is an alkyl group with 1 to 6 carbons, an alkenyl group with 3 to 6 carbons, benzyl or phenyl. The aforementioned phenyl groups may also be grouped by groups selected from 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 Substituted by at least one group.

(式中，*為鍵結處。) In formula (1), ^Q1 is a group represented by the following formula (Q1) or (Q2).

(In the formula, * is the bond.)

(式中，R ¹及R ²係與前述相同。*為鍵結處。) In formula (Q1), ^X2 is a group represented by formula (X1), formula (X2) or formula (X4). In formula (Q1), for example, when ^X2 is a group represented by formula (X2), its structure becomes the following formula (Q1-1).

(In the formula, R ¹ and R ² are the same as above. * is a bond.)

In the formula (Q2), ^Q2 is an alkylene group, a phenylene group, a naphthylene group or an anthracene group 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, hydroxyl, and 1 to 6 carbons. ~6 alkylthio groups are substituted by at least one group. Also, when ^Q2 is phenylene, naphthylene or anthracenyl, the bonding positions of these are not particularly limited. That is, for example, when the phenylene group is bonded at the 1-position and the 2-position, when the 1-position is bonded with the 3-position, or when the 1-position is bonded with the 4-position, the naphthylene group is bonded at the 1-position and the 2-position. In case of bonded position, bonded at 1-position and 4-position, bonded at 1-position and 5-position, or bonded at 2-position and 3-position, anthracenyl is bonded at 1-position and 2-position In the case of , in the case of bonding between the 1st and 4th positions, or in the case of bonding between the 9th and 10th positions, any of them may be used. n ¹ and n ² are each independently 0 or 1.

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

The above-mentioned alkoxy group having 1 to 6 carbon atoms may be any of linear, branched and cyclic, and specific examples thereof include, for example, methoxy, ethoxy, isopropoxy, n -pentyloxy, cyclohexyloxy, etc. The aforementioned alkylthio group having 1 to 6 carbons may be any of linear, branched, and cyclic, and specific examples thereof include methylthio, ethylthio, isopropylthio, n -pentylthio, cyclohexylthio and the like. As said halogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. are mentioned, for example. In addition, examples of the ring having 3 to 6 carbon atoms formed by combining ^R1 and ^R2 include, for example, a cyclobutane ring, a cyclopentane ring, and a cyclohexane ring.

The aforementioned alkylene group having 1 to 10 carbons may be any of linear, branched, and cyclic, and specific examples thereof include methylene, ethylidene, propylidene, and pentamethylene Methyl, cyclohexylene, 2-methylpropylidene, etc.

(式中，A ¹~A ⁶、R ¹~R ³及Q ¹係與前述相同。) Moreover, in formula (1), when X ¹ is a base shown in formula (X2), its structure then becomes what is shown in the following formula (1A), and when X ¹ is a base shown in formula (X3), its structure Then, it becomes what is shown by following formula (1B). Also, in the formula (X3), R ³ is preferably a 2-propenyl group.

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

In formula (1), Q ¹ preferably includes a cyclic structure from the viewpoint of the heat resistance of the aforementioned polyurea. That is, ^Q1 is a group represented by formula (Q1) or a group represented by formula (Q2) and ^Q2 is preferably cyclic alkylene, phenylene, naphthylene or anthracenyl, and The group represented by the formula (Q1) is preferable.

As the repeating unit represented by the formula (1), those represented by the following formulas (1-1) to (1-19) are preferable. In addition, in the following formulae, Me is a methyl group, and Et is an ethyl group.

The aforementioned polyurea system can be synthesized with reference to, for example, International Publication No. 2005/098542.

As the aforementioned acrylic polymer having a hydroxyl group or a carboxyl group, homopolymers such as acrylate homopolymers, methacrylate homopolymers, copolymers thereof, and polyacrylates having unsaturated double bonds with styrene or the like can be used. Copolymer of monomers.

As a preferable example of the aforementioned acrylic polymer, an acrylic polymer having a polyethylene glycol ester group or a hydroxyalkyl ester group having 2 to 6 carbon atoms can be mentioned. As such an acrylic polymer, as long as it is an acrylic polymer having such an arbitrary group, the skeleton (other repeating unit) constituting the main chain of the acrylic polymer, the type of side chain, and the like are not particularly limited.

As the acrylic polymer having a polyethylene glycol ester group or a hydroxyalkyl ester group having 2 to 6 carbon atoms, it is preferable to include a repeating unit represented by the following formula (2).

In formula (2), R ¹¹ is a hydrogen atom or a methyl group. R ¹² is a -(CH ₂ CH ₂ O) _n -H group or a hydroxyalkyl group with 2 to 6 carbons. n is an integer of 2 to 30, preferably an integer of 2 to 10.

Examples of the hydroxyalkyl group having 2 to 6 carbon atoms include 1-hydroxyethyl, 2-hydroxyethyl, 1-hydroxypropyl, 2-hydroxypropyl, 3-hydroxypropyl, 1-hydroxy Butyl, 2-hydroxybutyl, 3-hydroxybutyl, 4-hydroxybutyl, 2,3-dihydroxypropyl, etc.

Also, as long as the above-mentioned acrylic acid polymer does not impair the effect of the present invention, it may also contain repeating units other than the repeating unit represented by formula (2). The repeating unit of the monomer of the 6-hydroxyalkyl ester group.

The method for producing the aforementioned acrylic polymer is not particularly limited, for example, a monomer having at least one of a polyethylene glycol group and a hydroxyalkyl group having 2 to 6 carbons, and a monomer not having a polymer as necessary. The monomers of ethylene glycol ester group and hydroxyalkyl ester group with 2-6 carbon atoms are dissolved in a solution of a polymerization initiator in a solvent, and the polymerization reaction is carried out at a temperature of 50-110°C. The solvent to be used is not particularly limited as long as it can dissolve monomers, polymerization initiators, and the like.

Examples of the aforementioned monomer having a polyethylene glycol ester group include monoacrylate or monomethacrylate of H-(OCH ₂ CH ₂ ) _n -OH (n is the same as above). Examples of the aforementioned monomer having a hydroxyalkyl group having 2 to 6 carbon atoms include 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl methacrylate, acrylic acid 2-Hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, glycerol monoacrylate, glycerol monomethacrylate, etc.

Examples of monomers that do not have a polyethylene glycol ester group and a hydroxyalkyl ester group having 2 to 6 carbon atoms include carboxylic acid compounds such as acrylic acid and methacrylic acid, methyl acrylate, ethyl acrylate, Acrylate compounds such as propyl acrylate, isopropyl acrylate, butyl acrylate, isobutyl acrylate, t-butyl acrylate, phenyl acrylate, 4-hydroxyphenyl acrylate, methyl methacrylate, methyl Ethyl acrylate, propyl methacrylate, isopropyl methacrylate, butyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, phenyl methacrylate, Methacrylate compounds such as 4-hydroxyphenyl methacrylate, maleimide, N-methylmaleimide, N-phenylmaleimide, N-(4-hydroxybenzene base) Maleimide compounds such as maleimide and N-cyclohexylmaleimide, acrylamide compounds, methacrylamide compounds, acrylonitrile, maleic anhydride, styrene compounds, ethylene base compounds, etc.

Furthermore, the aforementioned acrylic polymer obtained by the aforementioned method is usually in a solution state dissolved in a solvent.

As a suitable example of the aforementioned acrylic polymer, for example, 2-hydroxyethyl acrylate, 2-hydroxyethyl methyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate , 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, glycerol monoacrylate, glycerol monomethacrylate and other hydroxyalkyl ester monomers are polymerized; The above-mentioned hydroxyalkyl ester monomers, and monomers other than these monomers, for example, selected from monomers that do not have a polyethylene glycol ester group and a hydroxyalkyl ester group with 2 to 6 carbon atoms. An acrylic polymer having a hydroxyalkyl group in a side chain, such as a polymer obtained by copolymerizing one or more monomers.

The aforementioned polyester having a hydroxyl group is not particularly limited, but one having an aromatic group or an alicyclic group in the main chain is preferable. Such a polyester is preferably a polyester obtained by reacting a compound having two or more epoxy group sites with a compound having two carboxyl groups.

Examples of the compound having two or more epoxy groups include bisphenol F diglycidyl ether, bisphenol A diglycidyl ether, bisphenol B diglycidyl ether, bisphenol AD Diglycidyl Ether, Bisphenol S Diglycidyl Ether, Tetrachlorobisphenol A Diglycidyl Ether, Catechin Diglycidyl Ether, Resorcinol Diglycidyl Ether , Hydroquinone Diglycidyl Ether, 1,5-Dihydroxynaphthalene Diglycidyl Ether, Dihydroxybiphenyl Diglycidyl Ether, Octachloro-4,4'-Dihydroxybiphenyl Di Glycidyl ether, Tetramethylbiphenyl Diglycidyl Ether, 9,9'-Bis(4-Hydroxyphenyl) Diglycidyl Ether, 9,9'-Bis(4-Hydroxy Bisphenol Diglycidyl Ether of Phenyl) Diglycidyl Ether, 9,9'-Bis(6-Hydroxy-2-naphthyl) Diglycidyl Ether, etc.; Ethylene Glycol Bicyclo Oxypropyl Ether, Propylene Glycol Diglycidyl Ether, Tetramethylene Glycol Diglycidyl Ether, 1,4-Butanediol Diglycidyl Ether, 1,6-Hexanediol Diglycidyl Ether Aliphatic diol diglycidyl ether such as propyl ether and neopentyl glycol diglycidyl ether; cyclohexanediol diglycidyl ether, cyclohexanedimethanol diglycidyl ether, Dicyclopentadiene Diol Diglycidyl Ether, Hydrogenated Bisphenol F Diglycidyl Ether, Hydrogenated Bisphenol A Diglycidyl Ether, Hydrogenated Bisphenol B Diglycidyl Ether, Hydrogenated Bisphenol S Diglycidyl ether, etc. Alicyclic diol diglycidyl ether; Diglycidyl phthalate, Diglycidyl isophthalate, Diglycidyl terephthalate, etc. Diglycidyl aromatic dicarboxylic acid ester; Diglycidyl oxalate, Diglycidyl adipate, Diglycidyl pimelate, 2-Ethyl-3-Propyl-1, Diglycidyl 5-pentanedioic acid and other alicyclic dicarboxylic acid diglycidyl esters; oxalic acid bis(3,4-epoxycyclohexylmethyl), adipate bis(3,4 -epoxycyclohexylmethyl), adipate bis(3,4-epoxy-6-methylcyclohexylmethyl), pimelate bis(3,4-epoxycyclohexylmethyl) , 2-ethyl-3-propyl-1,5-pentanedioic acid bis(3,4-epoxycyclohexylmethyl) and other diepoxidized alicyclic dicarboxylic acid diesters; ethylene dioxide Cyclohexene Dioxide, Limonene Dioxide, Dicyclopentadiene Dioxide, Epochalic (registered trademark) THI-DE, DE-102, DE-103 (manufactured by ENEOS Co., Ltd.), 3,4-Epoxycyclohexyl Methyl-3,4-epoxycyclohexanecarboxylate, alicyclic dioxide of 2,2-bis(3,4-epoxycyclohexyl)propane, etc. In addition, these compounds may be used alone or in combination of two or more.

Examples of compounds having two carboxyl groups include terephthalic acid, isophthalic acid, diphenic acid, 2-methylterephthalic acid, 2-hydroxyterephthalic acid, and 2,5-dimethylterephthalic acid. Terephthalic acid, 5-methylisophthalic acid, 5-hydroxyisophthalic acid, 2,6-naphthalene dicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid , 1,4-cyclohexanedicarboxylic acid, etc. In addition, these compounds may be used alone or in combination of two or more.

The method for synthesizing the aforementioned polyester is not particularly limited, and for example, a method of performing a polymerization reaction at a temperature of 50 to 150° C. in a solvent in which the aforementioned ester compound, carboxyl compound, and catalyst coexist. At this time, the solvent to be used is not particularly limited as long as it dissolves the aforementioned compound, polymerization initiator, and the like. The aforementioned polyester obtained by the aforementioned method is usually in a solution state dissolved in a solvent.

As said polyester, what contains the repeating unit represented by following formula (3) is preferable.

In formula (3), Y ¹ and Z ¹ are each independently a divalent group having an aromatic ring or an alicyclic ring.

(式中，*為鍵結處。) Y ¹ is preferably a group represented by the following formula (Y1-1).

(In the formula, * is the bond.)

In the formula (Y1-1), the L ^1s are each independently an ether bond or an ester bond. Y ² are each independently a divalent cyclic unsaturated hydrocarbon group with 3 to 10 carbons or a divalent cyclic saturated hydrocarbon group with 3 to 10 carbons. R ²¹ is a single bond, an ether bond, a carbonyl group, a sulfonyl group, a divalent saturated hydrocarbon group with 1 to 30 carbons, a divalent unsaturated hydrocarbon group with 2 to 30 carbons, or a 1 to 30 carbons substituted by a fluorine atom 2-valent saturated hydrocarbon group. p is 0, 1 or 2.

Y ² is preferably a divalent cyclic unsaturated hydrocarbon group with 4 to 16 carbons or a divalent cyclic saturated hydrocarbon group with 4 to 16 carbons, and a divalent cyclic unsaturated hydrocarbon group with 4 to 8 carbons or a carbon A divalent cyclic saturated hydrocarbon group with a number of 4 to 8 is preferred. Moreover, a part or all of the hydrogen atoms included in ^Y2 may be substituted by aliphatic groups, and a plurality of substituents among these may be combined with each other to form a 4-6 membered ring.

(式中，*為鍵結處。) Specific examples of ^Y2 include groups represented by the following formulas (Y2-1) to (Y2-12), but are not limited thereto.

(In the formula, * is the bond.)

Z ¹ is preferably an arylylene group having 6 to 20 carbons or a divalent cyclic saturated hydrocarbon group having 3 to 20 carbons. The aforementioned aryl group or divalent cyclic saturated hydrocarbon group may be substituted with a hydroxyl group, a methyl group, or the like.

(式中，*為鍵結處。) Specific examples of ^Z1 include groups represented by the following formulas (Z1-1) to (Z1-4), but are not limited thereto.

(In the formula, * is the bond.)

As the aforementioned polyester, one having a repeating unit represented by the following formula (4) is preferable.

In formula (4), Z ¹ is the same as above. The ring Cy is a tetravalent cyclic saturated hydrocarbon group having 4 to 20 carbon atoms or a tetravalent group represented by the following formula (Cy-1).

In the formula (Cy-1), Cy' is a trivalent cyclic saturated hydrocarbon group having 4 to 20 carbon atoms. R ³¹ is a divalent saturated hydrocarbon group with 1 to 20 carbons or a divalent unsaturated hydrocarbon group with 2 to 20 carbons, and may include an ester bond. *1 and *2 are bonding sites, and one of the two existing *1 and *2 is respectively bonded to a hydroxyl group.

The aforementioned 4-valent cyclic saturated hydrocarbon group and 3-valent cyclic saturated hydrocarbon group may be monocyclic or polycyclic, and in the case of polycyclic, may be condensed ring, cross-linked ring, spiro ring, or a plurality of such ring structures any one.

(式中，*1及*2為鍵結處，各構造式上存在之2個*1及*2之一者係分別與羥基鍵結。) Specific examples of the group represented by Cy include groups represented by the following formulas (Cy-2) to (Cy-8).

(In the formula, *1 and *2 are bonding sites, and one of the two *1 and *2 existing in each structural formula is respectively bonded to a hydroxyl group.)

Examples of the aforementioned cellulose having a hydroxyalkyl group or derivatives thereof include hydroxyalkyl celluloses such as hydroxyethyl cellulose and hydroxypropyl cellulose, hydroxyethyl methyl cellulose, hydroxypropyl cellulose, and hydroxypropyl cellulose. Hydroxyalkylalkylcelluloses such as methylcellulose and hydroxyethylethylcellulose, and derivatives thereof. Among them, hydroxyalkyl cellulose and their derivatives are preferable, and hydroxyethyl cellulose, hydroxypropyl cellulose, and their derivatives are more preferable. The aforementioned cellulose having a hydroxyalkyl group or its derivatives may be used alone or in combination of two or more.

The weight average molecular weight (Mw) of the component (B) is not particularly limited, but is preferably 1,000-500,000, more preferably 3,000-400,000, more preferably 5,000-300,000.

When the release layer forming composition of the present invention contains component (B), its content is preferably 0.1 to 100 parts by mass, more preferably 0.5 to 50 parts by mass, relative to 1 part by mass of component (A). good. If the content of the component (B) is within the aforementioned range, a peeling layer resin composition having high heat resistance, moderate peelability, and excellent stability after film formation can be obtained. (B) The component may be used individually by 1 type, and may use it in combination of 2 or more types.

[(C) Cross-linking agent] The composition for peeling layer formation of this invention may contain a crosslinking agent as (C)component as needed. The aforementioned crosslinking agent is selected from compounds having nitrogen atoms substituted with hydroxyalkyl groups and/or alkoxymethyl groups.

As the aforementioned crosslinking agent, a compound represented by any one of the following formulas (C-1) to (C-5) is preferred.

In formulas (C-1) to (C-5), R ¹⁰¹ to R ¹¹⁶ are each independently an alkyl group having 1 to 6 carbon atoms. ^RB is a hydrogen atom or a methyl group.

Specific examples of the aforementioned crosslinking agent include hexamethoxymethylmelamine, tetramethoxymethylbenzoguanamine, 1,3,4,6-tetra(methoxymethyl)acetylene carbamide, 1 , Nitrogen-containing compounds such as 3,4,6-tetra(butoxymethyl)acetylene carbamide and 1,3,4,6-tetra(hydroxymethyl)acetylene carbamide.

Also, methoxymethyl melamine compounds (trade names Cymel (registered trademark) 300, Cymel 301, Cymel 303, Cymel 350) manufactured by Allnex Corporation, butoxymethyl melamine compounds (trade names mycoat (registered trademark) 506, mycoat 508), acetylene carbamide compound (trade name Cymel1170, POWDERLINK 1174), methylated urea resin (trade name UFR65), butylated urea resin (trade name UFR300, U-VAN10S60, U-VAN10R, U-VAN11HV ), commercially available nitrogen-containing compounds such as urea/formaldehyde resins manufactured by DIC Co., Ltd. (trade names Beckamine (registered trademark) J-300S, Beckamine P-955, Beckamine N).

Also, as a crosslinking agent, N-hydroxymethyl (meth)acrylamide, N-methoxymethyl (meth)acrylamide, N-ethoxymethyl (meth)acrylamide, N-ethoxymethyl (meth)acrylamide, Polymers made from (meth)acrylamide compounds substituted with hydroxymethyl or alkoxymethyl groups such as amide and N-butoxymethyl (meth)acrylamide. Examples of such polymers include poly(N-butoxymethyl(meth)acrylamide), copolymers of N-butoxymethyl(meth)acrylamide and styrene, Copolymer of N-hydroxymethyl (meth)acrylamide and methyl (meth)acrylate, copolymer of N-ethoxymethylmethacrylamide and benzyl methacrylate, N- Copolymer of butoxymethyl (meth)acrylamide, benzyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate, etc.

As the aforementioned crosslinking agent, preferably, hexamethoxymethylmelamine, tetramethoxymethylbenzoguanamine, 1,3,4,6-tetra(methoxymethyl)acetylene carbamide (POWDERLINK 1174), 1,3,4,6-tetra(butoxymethyl)acetylene carbamide, 1,3,4,6-tetra(hydroxymethyl)acetylene carbamide.

These cross-linking agents are capable of causing a cross-linking reaction by self-condensation. Also, it can cause a crosslinking reaction with the hydroxyl group or carboxyl group in the resin of (A) or (B) component. And, by such a crosslinking reaction, the formed peeling layer becomes strong, and becomes a peeling layer whose solubility with respect to an organic solvent is low.

When the release layer forming composition of the present invention contains component (C), its content is preferably 1 to 1,000 parts by mass, preferably 2 parts by mass, relative to 100 parts by mass of component (A) when component (B) is not contained. ~800 parts by mass is better. When (B) component is contained, 5-200 mass parts is preferable with respect to a total of 100 mass parts of (A) component and (B) component, More preferably, it is 10-100 mass parts. (C) When the content of the component is within the above range, a peeling layer resin composition having high heat resistance and moderate peeling properties and excellent stability after film formation can be obtained. (C) The crosslinking agent may be used alone or in combination of two or more.

[(D) Cross-linking catalyst] The composition for peeling layer formation of this invention may contain a crosslinking catalyst as (D)component. As said crosslinking catalyst, a sulfonic acid compound, a carboxylic acid compound, and these salts are mentioned, for example.

Specific examples of the aforementioned sulfonic acid compound include, for example, p-toluenesulfonic acid, trifluoromethanesulfonic acid, pyridinium-p-toluenesulfonic acid salt, salicylic acid, camphorsulfonic acid, sulfosalicic acid, 4-chloro Benzenesulfonic acid, 4-hydroxybenzenesulfonic acid, benzenedisulfonic acid, 1-naphthalenesulfonic acid, pyridinium-1-naphthalenesulfonic acid, etc. Specific examples of the aforementioned carboxylic acid compound include salicylic acid, sulfalinic acid, citric acid, benzoic acid, hydroxybenzoic acid, and the like.

Examples of the salt of the aforementioned acid compound include pyridinium salts, isopropanolamine salts, and N-methylmorpholine salts of the aforementioned acids. Specific examples of the salt of the aforementioned sulfonic acid compound include, for example, p-pyridinium toluenesulfonate, pyridinium 1-naphthalenesulfonate, isopropanolamine p-toluenesulfonate, N-methylmorpholine p - Tosylate, etc. Specific examples of the salt of the aforementioned carboxylic acid compound include, for example, isopropanolamine salicylate, isopropanolamine sulfallic acid, and the like.

When the release layer forming composition of the present invention contains component (D), its content is preferably 0.01 to 100 parts by mass, preferably 0.1 parts by mass, relative to 100 parts by mass of component (A) when component (B) is not contained. ~80 parts by mass is better. When (B) component is contained, 0.01-15 mass parts is preferable with respect to the total 100 mass parts of (A) component and (B) component, and 0.1-10 mass parts is more preferable. If the content of the component (D) is within the above range, a release layer resin composition that can provide a release layer having high heat resistance and moderate releasability can be obtained. (D) The crosslinking catalyst system may be used individually by 1 type, and may use 2 or more types together.

[(E) Solvent] The composition for peeling layer formation of this invention may contain a solvent as (E) component. The aforementioned solvent is not particularly limited as long as it can dissolve the (A) component, and the necessary (B) component, (C) component, (D) component, and/or other additives described later. In the present invention, Glycol ether solvents with 3 to 20 carbon atoms, ester solvents with 3 to 20 carbon atoms, ketone solvents with 3 to 20 carbon atoms, and amide solvents are preferred.

Specific examples of the glycol ether solvent include propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether, and propylene glycol monopropyl ether. Specific examples of the aforementioned ester-based solvent include ethyl lactate, γ-butyrolactone, methyl 2-hydroxyisobutyrate, ethyl 2-hydroxyisobutyrate, and the like. Specific examples of the aforementioned ketone-based solvents include, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, and benzophenone. Specific examples of the aforementioned amide-based solvents include, for example, N-methylpyrrolidone, N,N-dimethylacetamide, 3-methoxy-N,N-dimethylpropanamide wait.

The content of the component (E) is preferably 0.1 to 40% by mass, more preferably 0.5 to 20% by mass, based on the solid content concentration in the composition for forming a peeling layer of the present invention. It is more preferably in an amount of 0.5 to 10% by mass. In addition, the solid content is a general term for all components of the composition for peeling layer formation, except for the solvent. (E) The solvent system may be used individually by 1 type, and may mix and use 2 or more types.

[other ingredients] The composition for peeling layer formation of this invention may contain surfactant as needed. By adding a surfactant, the coatability of the composition for forming a peeling layer to a substrate can be improved. As the surfactant, known surfactants such as nonionic surfactants, fluorine-based surfactants, and silicone-based surfactants can be used.

Specific examples of nonionic surfactants include, for example, polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene hexadecyl ether, polyoxyethylene oleyl ether, etc. Oxyethylene alkyl ethers; polyoxyethylene alkyl aryl ethers such as polyoxyethylene octylphenyl ether and polyoxyethylene nonylphenyl ether; polyoxyethylene and polyoxypropylene block copolymers; Alcohol monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan trioleate, sorbitan tristearate, etc. Sorbitan fatty acid esters; polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate esters, polyoxyethylene sorbitan fatty acid esters such as polyoxyethylene sorbitan tristearate, etc.

Specific examples of the aforementioned fluorine-based surfactants include Eftop (registered trademark) EF301, EF303, and EF352 (manufactured by Mitsubishi Materials Electron Chemicals Co., Ltd.), Megafac (registered trademark) F171, F173, F554, F559, and F563. , R-30, R-40, R-40-LM, DS-21 (manufactured by DIC), FLUORAD (registered trademark) FC430, FC431 (manufactured by 3M Corporation), Asahiguard (registered trademark) AG710, Surflon (registered Trademark) S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by AGC Co., Ltd.), etc.

Moreover, as a specific example of a silicone type surfactant, organosiloxane polymer KP341 (made by Shin-Etsu Chemical Co., Ltd.) etc. are mentioned, for example.

When the peeling layer forming composition of the present invention contains a surfactant, the content thereof is preferably 0.0001 to 1 part by mass, more preferably 0.001 to 0.5 part by mass, based on 100 parts by mass of component (A). . The aforementioned surfactants may be used alone or in combination of two or more.

In addition, the release layer-forming composition according to the embodiment of the present invention may contain silane coupling agents, rheology modifiers, pigments, dyes, storage stabilizers, antifoaming agents, antioxidants, etc., as long as the effects of the present invention are not impaired. as other additives.

[Preparation method of composition for peeling layer formation] The preparation method of the peeling layer forming composition of the present invention is not particularly limited, for example, to the solution of the (A) component dissolved in the solvent, mixing the necessary (B) in a predetermined ratio simultaneously or in an arbitrary order Component, (C) component and/or other components etc. to make a homogeneous solution. In addition, it is preferable to use the prepared solution of the peeling layer forming composition after filtering it with a filter having a pore diameter of about 0.2 μm or the like.

The viscosity of the peeling layer forming composition of the present invention is appropriately set in consideration of the thickness of the peeling layer to be produced, and especially when it is aimed at obtaining a film with a thickness of about 0.01 to 50 μm with good reproducibility, usually at At 25°C, 1~5,000mPa･s is better, and 1~2,000mPa･s is better.

Here, the viscosity can be measured using a commercially available viscometer for measuring liquid viscosity, for example, by referring to the method described in JIS K 7117-2, and measuring the temperature of the composition at 25°C. It is better to use a cone plate type (cone plate type) rotational viscometer as the viscometer, and it is better to use the same type of viscometer to use 1˚34'×R24 as the standard cone rotor, and to carry out under the condition of the temperature of the composition at 25°C Measurement. As such a rotational viscometer, Toki Sangyo Co., Ltd. TVE-25L is mentioned, for example.

[peeling layer] The peeling layer of the present invention can be obtained by including: a step of forming a resin film on a substrate using the aforementioned composition for peeling layer formation (resin film forming step), and a step of exposing a predetermined region of the aforementioned resin film with ultraviolet rays (exposure step) method to manufacture.

In the resin film forming step, as a method of forming the resin film, there may be mentioned, for example, a method of applying the composition for forming a release layer on a base and firing the composition. In addition, in the present invention, the base system means one whose surface is coated with the release layer-forming composition of the present invention, and which is used in the manufacture of flexible electronic devices and the like.

As the substrate, for example, glass, metal (silicon wafer, etc.), slate, etc. can be mentioned, especially because the peeling layer obtained from the composition for forming the peeling layer of the present invention has sufficient adhesion thereto , so glass is preferred. Furthermore, the base surface may be composed of a single material, or may be composed of two or more materials. As the aspect that the surface of the substrate is composed of two or more kinds of materials, if there are: the surface of the substrate, a certain range is composed of a certain material and the rest of the surface is composed of other materials, and the dot pattern on the entire surface of the substrate , Line width and line spacing pattern, etc., the state that the material with the shape of the pattern exists in other materials, etc.

The coating method is not particularly limited, and examples thereof include slit coating, cast coating, spin coating, knife coating, dip coating, roll coating, bar coating, and die coating. method, inkjet method, printing method (letterpanel, gravure, lithography, screen printing, etc.), etc.

As an appliance used for firing, a hot plate, an oven, etc. are mentioned, for example. The heating environment may be under air or an inert gas, and may be under normal pressure or reduced pressure.

The firing temperature is usually 50~250°C. Although the firing time cannot be uniformly specified because it varies depending on the temperature, it is usually 1 minute to 5 hours. Moreover, as long as the highest temperature falls into the said range in a baking process, you may include the process of baking at the temperature below that.

As a preferable example of the heating mode in the present invention, for example, after heating at 50-150°C for 1 minute-1 hour, directly raise the heating temperature and heat at 100-250°C for 5 minutes-4 hours appearance. In particular, as a more preferable example of the heating aspect, for example, an aspect of heating at 50 to 150° C. for 1 minute to 1 hour, and at 150 to 250° C. for 5 minutes to 2 hours is mentioned. Furthermore, as another preferred example of the heating aspect, for example, an aspect in which heating is performed at 200 to 250° C. for 5 minutes to 1 hour after heating at 50 to 150° C. for 1 minute to 30 minutes is exemplified.

In the aforementioned exposure step, the entire surface of the resin film may be irradiated with ultraviolet rays, or may be irradiated through a mask having a predetermined pattern. When irradiated through a mask, a release layer forming a pattern such as a dot pattern, a line width and a line pitch pattern, etc. can be obtained.

The aforementioned ultraviolet rays are not particularly limited as long as they are wavelengths capable of causing photo-Friesian rearrangement, and those with a wavelength of 200 to 400 nm are preferable, and specific examples thereof include 254 nm and the like. In addition, the irradiation dose is preferably 10~2,000mJ/cm ² , more preferably 50~1,000mJ/cm ² .

Furthermore, 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 on the entire surface. As an aspect in which a peeling layer is formed on a part of the substrate surface, if there is a pattern in which a peeling layer is formed only in a specified range on the substrate surface, a dot pattern, a line width and a line spacing pattern are used on the entire surface of the substrate or a specified range Etc. Figure shape to form the state of the peeling layer, etc.

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

The peeling layer of the present invention has excellent adhesion to substrates, especially glass substrates, and moderate adhesion and peelability to resin substrates. 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, and the resin substrate is peeled from the base together with the circuit formed on the resin substrate, Therefore, it can be used suitably.

[Manufacturing method of resin substrate] An example of a method of manufacturing a flexible electronic device using the release 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 predetermined region on a substrate by the aforementioned method. The peeling layer of the present invention is formed and fixed by applying a solution for forming a resin substrate for forming a resin substrate on the entire surface of the substrate on which the peeling layer has been formed in a designated area, and firing the obtained coating film. The base resin substrate.

The firing temperature of the above-mentioned coating film is appropriately set according to the type of resin, etc. The maximum temperature during firing is preferably 200~250°C, preferably 210~250°C, and 220~240°C for better. By setting the maximum temperature during firing of the resin substrate to this range, the adhesion between the release layer as the base and the substrate, or the appropriate adhesion and peelability between the release layer and the resin substrate can be further improved. Also in this case, as long as the maximum temperature falls within the aforementioned range, a step of firing at a temperature lower than that may also be included.

Examples of the resin substrate include a resin substrate made of a thermosetting film containing an epoxy compound, a resin substrate made of an acrylic polymer, and a resin substrate made of a cycloolefin polymer. The formation method of this resin substrate should just be performed according to a conventional method. Also, 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 above-mentioned resin substrate fixed to the base through the release layer of the present invention, a desired circuit is formed as necessary, and then, for example, the resin substrate is cut along the release layer, and the circuit is combined with the resin substrate. The resin substrate and the base are separated by peeling off the release layer. At this time, a part of the substrate may also be cut together with the release layer. When the peeling layer of the present invention is used, the resin substrate can be peeled from the peeling layer with a peeling force of 1.0 N/25 mm or less. [Example]

Hereinafter, the present invention will be described in more detail with reference to synthesis examples, preparation examples, working examples, and comparative examples, but the present invention is not limited to the following examples.

The compounds used in the following examples are as follows. PGME: Propylene Glycol Monomethyl Ether PGMEA: Propylene Glycol Monomethyl Ether Acetate PL-LI: 1,3,4,6-Tetra(methoxyethyl)acetylene carbamide (manufactured by Allnex, trade name: POWDERLINK 1174) PPTS: p-pyridinium toluenesulfonate MMA: methyl methacrylate HPMA: 2-Hydroxypropyl methacrylate HEMA: 2-Hydroxyethyl methacrylate ADMA: 2-adamantyl methacrylate DCPMA: Dicyclopentyl methacrylate PhMA: Phenyl methacrylate PhA: phenyl acrylate AcSt: 4-Acetyloxystyrene NMA: 2-Naphthyl Methacrylate HFiPMA: 1,1,1,3,3,3-Hexafluoroisopropyl methacrylate AIBN: Azobisisobutyronitrile DT: dodecanethiol

Also, the measurement of the weight average molecular weight (Mw) of the polymer was performed using a GPC device manufactured by Shimadzu Corporation (column: Shodex (registered trademark) KF803L and KF804L (manufactured by Showa Denko Co., Ltd.); eluent: THF, Flow rate: 1.0 mL/min, column temperature: 40° C., Mw: standard polystyrene conversion value).

[1] Synthesis of (A) component [Synthesis Example 1] By making HFiPMA 5.00g (21.18mmol), HPMA 1.53g (10.59mmol), PhMA 3.43g (21.18mmol), AIBN 0.54g (2.65mmol) as a polymerization catalyst, and DT 0.43g ( 2.65 mmol) was dissolved in 50.0 g of PGME, and reacted under heating and reflux for 20 hours to obtain a polymer solution. The obtained polymer solution was gradually dropped into a mixed solvent of 200 g of water and 200 g of methanol to deposit a solid. The precipitated solid was separated by filtration, and dried under reduced pressure to obtain a polymer (PA-1). The Mw of the acrylic copolymer (PA-1) was 6,400.

[Synthesis Example 2~7] Polymers (PA-2) to (PA-7) were obtained in the same manner as in Synthesis Example 1, except that the types and blending amounts of the raw material compounds were as shown in Table 1 below. Table 1 shows the Mw of the obtained polymer.

[2] Synthesis of (B) component [Synthesis Example 8] 50 g of monoallyldiglycidyl isocyanuric acid (manufactured by Shikoku Chemical Industry Co., Ltd.), 33.2 g of 5,5-diethylbarbituric acid, and 2.0 g of benzyltriethylammonium chloride g was dissolved in 341 g of PGME, and reacted at 130° C. for 24 hours to obtain a solution containing polyurea. The obtained solution containing polyurea was gradually dropped into 2,000 g of hexane to deposit a solid. The precipitated solid was separated by filtration, and dried under reduced pressure to obtain polyurea (L1). As a result of GPC analysis, the Mw of polyurea (L1) was 8,000.

[Synthesis Example 9] An acrylic copolymer solution was obtained by dissolving 100.0 g of MMA, 11.1 g of HEMA, and 5.6 g of AIBN as a polymerization catalyst in 450.0 g of PGME, and reacting at 80° C. for 20 hours. The obtained acrylic acid copolymer solution was dripped gradually on 5,000 g of hexane, and solid was deposited. The precipitated solid was separated by filtration and dried under reduced pressure to obtain an acrylic acid polymer (L2). As a result of GPC analysis, the Mw of the acrylic polymer (L2) was 7,600.

[3] Preparation of composition for resin substrate formation [Preparation Example 1] Preparation of Composition F1 for Resin Substrate Formation 10 g of Zeonoa (registered trademark) 1020R (cycloolefin polymer produced by Nippon Jain Co., Ltd.) and 3 g of Epolead (registered trademark) GT401 (manufactured by Daicel) were added to an eggplant-shaped flask containing 100 g of carbon tetrachloride. The solution was stirred and dissolved under a nitrogen atmosphere for 24 hours to prepare a composition F1 for forming a resin substrate.

[4] Preparation of composition for peeling layer formation [Example 1-1] Mix 7.5 parts by mass of polymer (PA-1) of component (A), 100 parts by mass of polyurea (L1) of component (B), 25 parts by mass of PL-LI of component (C), and 3 parts by mass of PPTS of component (D) Parts by mass, PGME:PGMEA=70:30 in terms of mass ratio, by adding PGME and PGMEA as a solvent, and preparing a peeling layer forming composition (A-1) with a solid content concentration of 5.0% by mass .

[Examples 1-2 to 1-7, Comparative Examples 1-1, 1-2] Except that the types and amounts of each component were set as described in Table 2, the peeling layer forming compositions A-2 to A-9 were prepared by the same method as in Example 1-1.

[5] Production of release layer and its evaluation [Example 2-1] Using a spin coater (condition: about 30 seconds at a rotation speed of 800 rpm), the composition (A-1) for forming a release layer was applied to On a glass substrate (Eagle XG manufactured by Corning Inc., 100 mm×100 mm×0.5 mm, the same below) as a base. 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 to form a peeling layer with a thickness of about 0.1 μm on the glass substrate. A part of the peeling layer was irradiated with ultraviolet light of 100 mJ/cm ² (254 nm conversion) including a 254 nm bright line using a high-pressure mercury lamp. Thereafter, the composition F1 for forming a resin substrate was coated on the entire surface of the glass substrate on which the peeling layer was formed in a designated region using a spin coater (condition: rotation speed: 200 rpm for about 15 seconds). Use a hot plate to heat the obtained coating film at 80°C for 2 minutes, and then use a hot plate to heat at 230°C for 30 minutes to form a resin substrate with a thickness of about 3 μm on the release layer to obtain a glass substrate with resin substrate and release layer.

[Examples 2-2 to 2-7, Comparative Examples 2-1, 2-2] Except for replacing the composition (A-1) for the formation of the peeling layer and using the compositions (A-2) to (A-9) for the formation of the peeling layer, the other systems were obtained using the same method as in Example 2-1. Examples 2-2~2-6, comparative examples 2-1 and 2-2 are glass substrates with resin substrates and peeling layers.

[Evaluation of Peeling Force] Use a cutter to engrave short strips of 25mm x 50mm on the glass substrates with resin substrates and peeling layers obtained in Examples 2-1~2-7, Comparative Examples 2-1 and 2-2. Also, after affixing Cellotape (registered trademark) (Nichiban Co., Ltd. CT-24), use Autograph AGS-X500N (manufactured by Shimadzu Corporation) to peel off at a peeling angle of 90° and a peeling speed of 300mm/min. And measure the peel force. The evaluation results are collectively shown in Table 3 as "peeling force".

According to the results shown in Table 3, compared with the peeling layer of the example, the peeling force was lower in the unexposed part, but the peeling force was higher in the exposed part than in the unexposed part. On the other hand, the peeling layer of the comparative example exhibited low peeling force regardless of exposure.

Claims (13)

A composition for forming a release layer, comprising (A) a polymer comprising a repeating unit having a photosensitive group that causes photo-Fries rearrangement. The composition for forming a peeling layer according to claim 1, wherein the repeating unit having a photosensitive group that causes photo-Fries rearrangement is derived from a monomer represented by the following formula (a1) or (a2);

In the formula, Ar ^is phenyl, 1-naphthyl, 2-naphthyl, 2-biphenyl, 3-biphenyl or 4-biphenyl, and a part or all of the hydrogen atoms of these bases can be replaced by carbon Alkyl groups with a number of 1 to 6, alkoxy groups with a carbon number of 1 to 6, chlorine atoms or bromine atoms, but at least one of the ortho and para positions of the oxygen atom in the formula is a hydrogen atom; Ar ² is 1 ,2-phenylene, 1,3-phenylene, 1,4-phenylene, 1,2-naphthyl, 1,3-naphthyl, 1,4-naphthyl, 1,5 -Naphthyl, 1,6-naphthyl, 1,7-naphthyl, 1,8-naphthyl, 2,3-naphthyl, 2,6-naphthyl, 2,2'- Biphenylene, 2,3'-biphenylene, 2,4'-biphenylene, 3,3'-biphenylene, 3,4'-biphenylene or 4, 4'-biphenylene, a part or all of the hydrogen atoms of these groups may be replaced by an alkyl group with 1 to 6 carbons, an alkoxy group with 1 to 6 carbons, a chlorine atom or a bromine atom. At least one of the ortho and para positions of the oxygen atom is a hydrogen atom, R ¹ is an alkyl or phenyl group with 1 to 6 carbons; X ¹ and X ² are each independently a single bond or an extension with 1 to 20 carbons Alkyl, one or more -CH ₂ - of the alkylene group may be substituted by at least one group selected from -O-, -C(=O)-O- and -OC(=O)-; ^A1 and ^A2 are each independently a radically polymerizable group containing a carbon-carbon double bond. The resin composition for forming a release layer according to claim 2, wherein the radical polymerizable group is represented by any one of the following formulas (A-1) to (A-4);

R ^A is each independently a hydrogen atom or a methyl group. The resin composition for forming a release layer according to claim 1 or 2, wherein (A) polymer is a repeating unit derived from a monomer represented by the following formula (b) and derived from a monomer represented by the following formula (c) Polymers of repeating units of monomers;

In the formula, R ^A is each independently a hydrogen atom or a methyl group; R ^B is a branched alkyl group with 3 or 4 carbons in which at least one hydrogen atom is replaced by a fluorine atom; R ^C is a branched alkyl group with 2 to 10 carbons Hydroxyalkyl. The composition for forming a release layer according to any one of claims 1 to 4, further comprising (B) a resin having a hydroxyl group or a carboxyl group. The composition for forming a release layer according to any one of claims 1 to 5, wherein (B) the resin having a hydroxyl group or a carboxyl group is a polyurea having a hydroxyl group, an acrylic polymer having a hydroxyl group or a carboxyl group, or a polyester having a hydroxyl group, Or cellulose or derivatives thereof having a hydroxyalkyl group. The composition for forming a release layer according to any one of Claims 1 to 6, which further includes (C) a crosslinking agent, and the (C) crosslinking agent is selected from Compounds with substituted nitrogen atoms. The composition for forming a release layer according to any one of claims 1 to 7, further comprising (D) a crosslinking catalyst. A release layer obtained from the composition for forming a release layer according to any one of claims 1 to 8. A laminate comprising a resin layer laminated on the peeling layer as claimed in claim 9, and the light transmittance of the resin layer at a wavelength of 400 nm is more than 80%. The laminate according to claim 10, wherein the resin substrate is a thermosetting film containing an epoxy compound. A method for forming a release layer, comprising: using the composition for forming a release layer according to any one of claims 1 to 8 to form a resin film on a substrate, and exposing a predetermined area of the resin film with ultraviolet rays step. A method of manufacturing a resin substrate, comprising: the step of forming a resin film on a substrate using the composition for forming a peeling layer according to any one of claims 1 to 8, the step of exposing a predetermined area of the resin film with ultraviolet rays, A step of forming a resin substrate with a light transmittance of 400nm at a wavelength of 80% or more on the release layer, and a step of peeling the resin substrate formed on the release layer with a peeling force of 1.0N/25mm or less.