JP2022140914A - Release layer-forming composition and release layer - Google Patents

Abstract

To provide a release layer-forming composition that allows a device composed of a resin substrate or the like to be formed on a release layer, ensuring easy release at an interface between the release layer and the device composed of the resin substrate or the like.SOLUTION: A release layer-forming composition contains (A) a polymer derived from a monomer having an epoxy group (constitutional unit (a)), with the content of the constitutional unit (a) being 1-30 mol% relative to all the monomer units of 100 mol%, and the polymer having a glass transition point of 25°C or higher.SELECTED DRAWING: None

Description

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

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

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

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

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

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

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

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

As a result of intensive studies to achieve the above object, the present inventors have found that (A) a polymer obtained by using a monomer having an epoxy group (structural unit (a)), A composition for forming a release layer containing a polymer having a content of 1 to 30 mol % with respect to 100 mol % of the total monomer units and a glass transition point of 25° C. or higher is applied to a resin substrate or the like on the release layer. The present inventors have found that a device can be formed from a device composed of a resin substrate or the like, and a release layer that can be easily peeled off at the interface between the release layer and a device composed of a resin substrate or the like can be provided with good reproducibility, and the present invention has been completed.

That is, the present invention provides the following release layer-forming composition and release layer.
1. (A) A polymer obtained by using a monomer having an epoxy group (structural unit (a)), wherein the content of the structural unit (a) is 1 to 30 mol% relative to 100 mol% of the total monomer units. A composition for forming a release layer containing a polymer having a glass transition point of 25° C. or higher.
2. (A) The polymer is a polymer obtained using a monomer selected from the group consisting of acrylic acid ester compounds, methacrylic acid ester compounds, maleimide compounds, acrylamide compounds, acrylonitrile, maleic anhydride, styrene compounds and vinyl compounds. The resin composition for forming a release layer according to claim 1.
3. (B) 1 or 2 of the release layer-forming resin composition further containing a cross-linking agent.
4. (B) The resin composition for forming a release layer according to any one of 1 to 3, wherein the cross-linking agent is a cross-linking agent having an epoxy group.
5. (C) The release layer-forming resin composition according to any one of 1 to 4, further containing a crosslinking catalyst.
6. (C) The resin composition for forming a release layer of 5, wherein the cross-linking catalyst is a thermal acid generator or a photoacid generator.
7. (B) The resin composition for forming a release layer according to any one of 3 to 6, wherein the content of the crosslinking agent is 1 to 50 parts by mass with respect to 100 parts by mass of the polymer (A).
8. (C) The resin composition for forming a release layer according to any one of 5 to 7, wherein the content of the crosslinking catalyst is 0.01 to 20 parts by mass based on 100 parts by mass of the polymer (A).
9. A release layer obtained from the release layer-forming resin composition of any one of 1 to 8.
10. A laminated body in which a resin substrate having a light transmittance of 80% or more at a wavelength of 400 nm is laminated on the release layer of No. 9.
11. 10. A laminate according to 10, wherein the resin substrate is a thermosetting film containing an epoxy compound.
12. applying the composition for forming a release layer according to any one of 1 to 8 to a substrate to form a release layer;
Manufacture of a resin substrate, comprising the steps of: forming a resin substrate having a light transmittance of 80% or more at a wavelength of 400 nm on the peeling layer; and peeling the resin substrate with a peeling force of 0.4 N/25 mm or less. Method.

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

The present invention will be described in more detail below.
[Composition for forming release layer]
The release layer-forming composition of the present invention is a polymer obtained by using (A) a monomer having an epoxy group (structural unit (a)), and the content of the structural unit (a) is 100 total monomer units. It is characterized by containing a polymer having a glass transition point of 25° C. or higher in an amount of 1 to 30 mol % based on mol %.

[1] Component (A) The component (A) in the release layer-forming composition of the present invention is a polymer obtained using a monomer having an epoxy group (structural unit (a)). is 1 to 30 mol % with respect to 100 mol % of all monomer units, and the glass transition point is 25° C. or higher.

The monomer having an epoxy group of the structural unit (a) is not particularly limited as long as it is a monomer having an epoxy group in the molecule. compounds, acrylonitrile, maleic anhydride, styrene compounds and vinyl compounds.

Specific examples of the monomer having an epoxy group in the structural unit (a) include glycidyl acrylate, glycidyl methacrylate, 4-hydroxybutyl acrylate glycidyl ether, glycidyl α-ethyl acrylate, 3,4-epoxycyclohexylmethylmethacrylate, acrylates, α-n-propyl glycidyl acrylate, α-n-butyl glycidyl acrylate, 3,4-epoxybutyl acrylate, 3,4-epoxybutyl methacrylate, 6,7-epoxyheptyl acrylate, 6,7-epoxyheptyl methacrylate, 6,7-epoxyheptyl α-ethyl acrylate, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether and the like.

The polymer of component (A) in the release layer-forming composition of the present invention may contain a monomer having no epoxy group (structural unit (b)).
As the monomer for the structural unit (b), any monomer that can be copolymerized with the epoxy group-containing monomer and that is inert to the epoxy group, that is, does not have a group that reacts with the epoxy group. There are no particular restrictions, and examples thereof include acrylic acid ester compounds, methacrylic acid ester compounds, maleimide compounds, acrylamide compounds, acrylonitrile, maleic anhydride, styrene compounds, and vinyl compounds.

Specific examples of acrylic ester compounds include methyl acrylate, ethyl acrylate, isopropyl acrylate, benzyl acrylate, naphthyl acrylate, anthryl acrylate, anthryl methyl acrylate, phenyl acrylate, glycidyl acrylate, 2,2,2-trifluoroethyl acrylate. , tert-butyl acrylate, cyclohexyl acrylate, isobornyl acrylate, 2-methoxyethyl acrylate, methoxytriethylene glycol acrylate, 2-ethoxyethyl acrylate, tetrahydrofurfuryl acrylate, 3-methoxybutyl acrylate, 2-methyl-2-adamantyl acrylates, 2-propyl-2-adamantyl acrylate, 8-methyl-8-tricyclodecyl acrylate, 8-ethyl-8-tricyclodecyl acrylate and the like.

Specific examples of methacrylate ester compounds include methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, benzyl methacrylate, naphthyl methacrylate, anthryl methacrylate, anthryl methyl methacrylate, phenyl methacrylate, glycidyl methacrylate, and 2,2,2-trifluoroethyl methacrylate. , tert-butyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, 2-methoxyethyl methacrylate, methoxytriethylene glycol methacrylate, 2-ethoxyethyl methacrylate, tetrahydrofurfuryl methacrylate, 3-methoxybutyl methacrylate, stearyl methacrylate, adamantyl methacrylate, 2 -methyl-2-adamantyl methacrylate, γ-butyrolactone methacrylate, 2-propyl-2-adamantyl methacrylate, 8-methyl-8-tricyclodecyl methacrylate, 8-ethyl-8-tricyclodecyl methacrylate and the like.

Specific examples of vinyl compounds include methyl vinyl ether, benzyl vinyl ether, vinylnaphthalene, vinylcarbazole, allyl glycidyl ether, 3-ethenyl-7-oxabicyclo[4.1.0]heptane, 1,2-epoxy-5-hexene. , 1,7-octadiene monoepoxide and the like.
Specific examples of styrene compounds include styrene, methylstyrene, chlorostyrene, bromostyrene and the like.
Specific examples of maleimide compounds include maleimide, N-methylmaleimide, N-phenylmaleimide, N-cyclohexylmaleimide and the like.

From the viewpoint of heat resistance and hydrophobicity, the monomer of the structural unit (b) is preferably a (meth)acrylic acid ester compound or a maleimide compound having an alicyclic hydrocarbon group. The alicyclic hydrocarbon group is more preferably an alicyclic hydrocarbon group having 6 to 20 carbon atoms, such as cyclohexyl group, t-butylcyclohexyl group, isobornyl group, dicyclopentanyl group, dicyclopentenyl group, Adamantyl groups may be mentioned.

Specific examples of (meth)acrylic acid ester compounds having an alicyclic hydrocarbon group include isobornyl methacrylate, isobornyl acrylate, dicyclopentanyl methacrylate, dicyclopentanyl acrylate, dicyclopentenyl methacrylate, dicyclo Pentenyl acrylate, adamantyl methacrylate, cyclohexyl methacrylate, t-butylcyclohexyl methacrylate and the like can be mentioned.

The glass transition temperature (Tg) of the resulting polymer is 25° C. or higher, preferably 50° C. or higher, more preferably 100° C. or higher. By setting the glass transition temperature of the polymer to 25° C. or higher, the heat resistance of the release layer tends to be favorably improved.

The glass transition temperature of the polymer means a calculated value calculated by the following Fox formula (see Bull. Am. Phys. Soc., 1(3) 123 (1956)). The Fox formula below shows the formula when the polymer is a copolymer of monomer i (monomer 1, monomer 2, . . . , and monomer n).
₁ /Tg ₌ W1 _/ Tg1 ₊ W2/Tg2+...+ _Wn / _Tgn
Tg: glass transition temperature of the polymer (unit: K)
W _n : mass fraction of monomer n with respect to the total amount of monomers constituting the polymer Tg _n : glass transition temperature of homopolymer of monomer n (unit: K)

For the glass transition temperature (Tg _n ) of the homopolymer, values described in various literatures can be adopted. For example, the values described in "POLYMER HANDBOOK 3rd Edition" (published by John Wiley & Sons, Inc.) are adopted can. For those not described in the literature, the value of the glass transition temperature measured by the DSC method of a homopolymer obtained by polymerizing a monomer by a conventional method can be adopted.

(A) In a polymer containing a predetermined repeating unit, the content of the monomer of the structural unit (a) is 1 to 30 mol%, preferably 2 to 25 mol%, of the total repeating units. When the monomer content of the structural unit (a) of the cross-linking agent is too small, the solvent resistance and heat resistance of the release layer are lowered, and the releasability is lowered. On the other hand, if the content is too high, the reaction with the resin substrate or the like on the release layer may proceed, resulting in a decrease in release properties. The monomers of the structural unit (a) and the structural unit (b) may be used singly or in combination of two or more.

The method for obtaining the polymer used in the release layer-forming composition of the present invention is not particularly limited. It is obtained by a polymerization reaction at a temperature of 50 to 110° C. in the medium. At that time, the solvent used is not particularly limited as long as it dissolves the monomer of the structural unit (a), the monomer of the structural unit (b), the polymerization initiator, and the like. Specific examples thereof include the solvents described in the solvent to be described later.

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

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

In the release layer-forming composition of the present invention, the powder of the polymer may be used as the component (A) as it is, or the powder may be redissolved in a solvent described later, for example, and used in the form of a solution. may

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

[2] Component (B) The release layer-forming composition of the present invention may optionally contain a cross-linking agent as component (B). The cross-linking agent is a compound that can react with the polymer of component (A) to form a cross-linked structure, or a compound that can contribute to the formation of a cross-linked structure, such as a compound that can react with itself to form a cross-linked structure. Although not particularly limited, it is preferable to use a compound having an epoxy group as a cross-linking agent in the present invention.

The cross-linking agent having an epoxy group includes compounds having two or more epoxy groups. Such compounds may be low-molecular-weight compounds or high-molecular-weight compounds.

Specific examples of low-molecular-weight compounds having two or more epoxy groups include tris(2,3-epoxypropyl)isocyanurate, 1,4-butanediol diglycidyl ether, and 1,2-epoxy-4-(epoxyethyl). Cyclohexane, glycerol triglycidyl ether, diethylene glycol diglycidyl ether, 2,6-diglycidylphenyl glycidyl ether, 1,1,3-tris[p-(2,3-epoxypropoxy)phenyl]propane, 1,2-cyclohexanedicarbon acid diglycidyl ester, 4,4′-methylenebis(N,N-diglycidylaniline), 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate, trimethylolethane triglycidyl ether, bisphenol-A-di Examples include glycidyl ether, pentaerythritol polyglycidyl ether, and compounds represented by the following formula (1).

（式中、ｋは２～１０の整数、ｍは０～４の整数を示し、Ｒ¹はｋ価の有機基を表す）

(Wherein, k is an integer of 2 to 10, m is an integer of 0 to 4, and R ¹ represents a k-valent organic group)

Specific examples of the compound represented by formula (1) include compounds represented by the following formulas (C1-1) and (C1-2).

Commercially available compounds containing two or more epoxy groups include Epolead GT-401, Epolead GT-403, Epolead GT-301, Epolead GT-302, Celoxide 2021 and Celoxide 3000 (manufactured by Daicel Chemical Industries, Ltd.). Epikote 1001, Epikote 1002, Epikote 1003, Epikote 1004, Epikote 1007, Epikote 1009, Epikote 1010, Epikote 828 (manufactured by Mitsubishi Chemical Corporation) and other bisphenol A type epoxy compounds , bisphenol F type epoxy compounds such as Epicoat 807 (manufactured by Mitsubishi Chemical Co., Ltd.), Epicoat 152, Epicoat 154 (manufactured by Mitsubishi Chemical Co., Ltd.), EPPN201, EPPN202 (manufactured by Nippon Kayaku Co., Ltd.), etc. ECON-102, ECON-103S, ECON-104S, ECON-1020, ECON-1025, ECON-1027 (manufactured by Nippon Kayaku Co., Ltd.), Epicoat 180S75 (Mitsubishi Chemical Co., Ltd.) ), Denacol EX-252 (manufactured by Nagase ChemteX Co., Ltd.), CY175, CY177, CY179, Araldite CY-182, Araldite CY-192, Araldite CY-184 (above, CIBA-GEIGY AG), Epiclon 200, Epiclon 400 (manufactured by DIC Corporation) Epicort 871, Epicort 872 (manufactured by Mitsubishi Chemical Corporation) ED-5661, ED-5662 (manufactured by Celanese Coating Co., Ltd.) ), Denacol EX-611, Denacol EX-612, Denacol EX-614, Denacol EX-622, Denacol EX-411, Denacol EX-512, Denacol EX-522, Denacol EX-421 , Denacol EX-313, Denacol EX-314, and Denacol EX-312 (manufactured by Nagase ChemteX Corporation).

Among the compounds having two or more epoxy groups, compounds having two or more cyclohexene oxide structures are preferable from the viewpoint of cross-linking reactivity, heat resistance, solvent resistance, long-term baking resistance, etc., and the above formula (1) Compounds represented by formula (C1-1), compounds represented by formula (C1-2), Epolead GT-401, GT-403, GT-301, GT-302 , Celoxide 2021 and Celoxide 3000 are more preferred.

These cross-linking agents can cause a cross-linking reaction by self-condensation. In addition, it can cause a cross-linking reaction with epoxy groups in the polymer of component (A). By such a cross-linking reaction, the formed release layer is strengthened and becomes a release layer having high resistance to organic solvents, heat resistance, and long-term baking resistance.

When component (B) is used, its content is preferably 1 to 50 parts by mass, more preferably 2 to 40 parts by mass, more preferably 3 to 30 parts by mass, relative to 100 parts by mass of the polymer of component (A). preferable. When the content of component (B) is within the above range, a release layer resin composition having high heat resistance and appropriate release properties can be obtained. When the content of the cross-linking agent is too small, the solvent resistance and heat resistance of the release layer are lowered, and the releasability is lowered. On the other hand, if the content is excessively high, the cross-linking reaction with the resin substrate or the like on the release layer may proceed and the release property may deteriorate. (B) The crosslinking agent may be used singly or in combination of two or more.

[3] (C) Component The release layer-forming composition of the present invention may contain a crosslinking catalyst as the (C) component. As the cross-linking catalyst, a thermal acid generator or a photoacid generator is preferable.

The thermal acid generator is a catalyst that generates an acid by heating and cationic polymerization of epoxy groups by the action of the acid.
The thermal acid generator is not particularly limited as long as it can generate an acid by heat, and examples thereof include onium salts such as sulfonium salts, benzothiazolium salts, ammonium salts and phosphonium salts.

Specific examples of thermal acid generators include benzyl(4-hydroxyphenyl)methylsulfonium, (4-acetoxyphenyl)dimethylsulfonium, (4-hydroxyphenyl)dimethylsulfonium, (2-methylbenzyl)(4-hydroxyphenyl) a cation selected from methylsulfonium, (1-naphthylmethyl)(4-hydroxyphenyl)methylsulfonium and benzyl(4-acetoxyphenyl)methylsulfonium, and tris(pentafluoroethyl)trifluorophosphate, hexafluorophosphate, tetrafluoroborate , tetrakis(pentafluorophenyl)borate, hexafluoroantimonate, p-toluenesulfonate, dodecylbenzenesulfonate, trifluoromethanesulfonate, and perfluorobutanesulfonate.

Commercially available products can be used as the thermal acid generator, and specific examples include TA-60, TA-60B, TA-100, TA-120, TA-160 (manufactured by San-Apro Co., Ltd.), K -PURE (registered trademark) TAG-2678, TAG-2681, TAG-2689, TAG-2690, TAG-2700, CXC-1612, CXC-1614, CXC-1615, CXC-1616, The same CXC-1733, the same CXC-1738, the same CXC-1742, the same CXC-1802, the same CXC-1821 (manufactured by King Industries Inc.), the same San-Aid SI-45, the same SI-45L, the same SI-60, the same SI-60L, SI-80, SI-80L, SI-100, SI-100L, SI-110, SI-110L, SI-150, SI-150L, SI-180, SI-180L, SI-B2, SI-B2A, SI-B3, SI-B3A, SI-B4, SI-B5, SI-200, SI-210, SI-220, SI-300, SI-360 (manufactured by Sanshin Chemical Industry Co., Ltd.) and the like.

The photoacid generator is a catalyst that generates an acid when irradiated with light and causes cationic polymerization of epoxy groups by the action of the acid.
Examples of photoacid generators include sulfonium salt compounds, iodonium salt compounds, phosphonium salts, disulfone compounds, imidosulfonate compounds, halogen-containing triazine compounds, acetophenone derivative compounds, and cyano group-containing oxime sulfonate compounds.

Specific examples of photoacid generators include 2-butenyldimethylsulfonium, 2-butenyltetramethylenesulfonium, 3-methyl-2-butenyldimethylsulfonium, 4-hydroxyphenylcinnamylmethylsulfonium, α-naphthylmethyltetra methylenesulfonium, cinnamyldimethylsulfonium, cinnamyltetramethylenesulfonium, biphenylmethyldimethylsulfonium, biphenylmethyltetramethylenesulfonium, phenylmethyldimethylsulfonium, phenylmethyltetramethylenesulfonium, fluorenylmethyldimethylsulfonium, fluorenylmethyltetramethylenesulfonium , bis[4-(diphenylsulfonio)phenyl]sulfide, diphenyl-4-(phenylthio)phenylsulfonium, triphenylsulfonium, bis[4-(di(4-(2-hydroxyethoxy))phenylsulfonio)phenyl] a cation selected from sulfide, benzyl(4-hydroxyphenyl)methylsulfonium, dibenzyl-4-hydroxyphenylsulfonium, 4-acetoxyphenylbenzylsulfonium and the like, and tris(pentafluoroethyl)trifluorophosphate, hexafluorophosphate, tetrafluoroborate , tetrakis(pentafluorophenyl)borate, hexafluoroantimonate, p-toluenesulfonate, dodecylbenzenesulfonate, trifluoromethanesulfonate and perfluorobutanesulfonate sulfonium salts which are salts of anions; diphenyliodonium chloride, diphenyl Iodonium trifluoromethanesulfonate, diphenyliodonium mesylate, diphenyliodonium tosylate, diphenyliodonium bromide, diphenyliodonium tetrafluoroborate, diphenyliodonium hexafluoroantimonate, diphenyliodonium hexafluoroarsenate, bis(p-tert-butylphenyl)iodonium hexa Fluorophosphate, bis(p-tert-butylphenyl)iodonium mesylate, bis(p-tert-butylphenyl)iodonium tosylate, bis(p-tert-butylphenyl)iodonium trifluoromethanesulfonate, bis(p-tert-butyl Phenyl)iodonium tetrafluorobore iodonium salts such as bis(p-tert-butylphenyl)iodonium chloride, bis(p-chlorophenyl)iodonium chloride, bis(p-chlorophenyl)iodonium tetrafluoroborate; triphenylphosphonium chloride, triphenylphosphonium bromide, tri( Phosphonium salts such as p-methoxyphenyl)phosphonium tetrafluoroborate, tri(p-methoxyphenyl)phosphonium hexafluorophosphonate, tri(p-ethoxyphenyl)phosphonium tetrafluoroborate; disulfone compounds such as di(phenylsulfone); N- (methylsulfonyloxy)succinimide, N-(methylsulfonyloxy)phthalimide, N-(methylsulfonyloxy)diphenylmaleimide, N-(methylsulfonyloxy)bicyclo[2.2.1]hept-5-ene-2,3 -dicarboximide, N-(methylsulfonyloxy)bicyclo[2.2.1]heptane-5,6-oxy-2,3-dicarboximide, N-(methylsulfonyloxy)naphthyldicarboximide, etc. Sulfonate compounds; the methylsulfonyloxy of their imidosulfonate compounds to propylsulfonyloxy, butylsulfonyloxy, camphorsulfonyloxy, p-toluenesulfonyloxy, 2-trifluoromethylphenylsulfonyloxy, 4-fluorophenylsulfonyloxy and trifluoromethyl Examples thereof include compounds substituted with a group selected from sulfonyloxy groups.

Commercially available products can be used as the photoacid generator, and specific examples include San-Aid SI-45L, San-Aid SI-60L, San-Aid SI-80L, San-Aid SI-100L, San-Aid SI-110L, San-Aid SI-150L ( Above, manufactured by Sanshin Chemical Industry Co., Ltd.), Adeka Optomer SP-150, Adeka Optomer SP-170, Adeka Optomer SP-171 (manufactured by ADEKA Co., Ltd.), UVE-1014 (manufactured by General Electronics Co., Ltd.) ), CD-1012 (manufactured by Sartomer) and the like.

When component (C) is used, its content is preferably 0.01 to 20 parts by mass, more preferably 0.1 to 20 parts by mass, more preferably 0.1 to 100 parts by mass of the polymer of component (A). ~10 parts by mass is even more preferred. When the content of component (C) is within the above range, a release layer resin composition having high heat resistance and appropriate release properties can be obtained. In addition, (C) crosslinking catalyst may be used individually by 1 type, and may be used in combination of 2 or more types.

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

Specific examples of nonionic surfactants include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, and polyoxyethylene oleyl ether; Ethers, polyoxyethylene alkylaryl ethers such as polyoxyethylene nonylphenyl ether; polyoxyethylene/polyoxypropylene block copolymers; sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate, sorbitan Sorbitan fatty acid esters such as trioleate and sorbitan tristearate; polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, polyoxyethylene sorbitan trioleate polyoxyethylene sorbitan fatty acid esters such as stearate;

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

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

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

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

[5] Solvent The release layer-forming composition of the present invention may contain a solvent.
The type and structure of the solvent are particularly limited as long as it has the ability to dissolve the component (A), the components (B) and (C) that are used as necessary, and other additives. However, 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 glycol ether solvents include propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether, and propylene glycol monopropyl ether.
Specific examples of ester solvents include ethyl lactate, γ-butyrolactone, methyl 2-hydroxyisobutyrate, and ethyl 2-hydroxyisobutyrate.
Specific examples of ketone-based solvents include methyl ethyl ketone, cyclohexanone, cyclopentanone, and benzophenone.
Specific examples of amide solvents include N-methylpyrrolidone, N,N-dimethylacetamide, 3-methoxy-N,N-dimethylpropanamide and the like.
In addition, a solvent may be used individually by 1 type, and may be used in combination of 2 or more type.

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

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

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

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

[Release layer]
A release layer can be obtained by a baking method including a step of applying the release layer-forming composition of the present invention onto a substrate and then baking the composition at 100 to 250°C.
In this case, the sintering time varies depending on the temperature and cannot be generally specified, but is usually 1 minute to 5 hours. Moreover, the firing step may include a step of firing at a temperature lower than the maximum temperature, as long as the maximum temperature falls within the above range.

A preferred example of the heating mode in the present invention includes heating at 50 to 150° C. for 1 minute to 1 hour and then increasing the heating temperature to 100 to 250° C. for 5 minutes to 4 hours. In particular, a more preferable heating mode is heating at 50 to 150° C. for 1 minute to 1 hour and heating at 150 to 250° C. for 5 minutes to 2 hours. Furthermore, another more preferable example of the heating mode includes heating at 50 to 150° C. for 1 minute to 30 minutes and then heating at 200 to 250° C. for 5 minutes to 1 hour.

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

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

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

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

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

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

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

The baking temperature of the coating film is appropriately set according to the type of resin, etc., but in the present invention, the maximum temperature during baking is preferably 200 to 250 ° C., and 210 to 250 ° C. is more preferable, and 220 to 240° C. is even more preferable. By setting the maximum baking temperature in this range for the production of the resin substrate, it is possible to further improve the releasability between the release layer and the resin substrate. Also in this case, as long as the maximum temperature falls within the above range, a step of firing at a temperature lower than that may be included.

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

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

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

Abbreviations used in the following examples have the following meanings.

[Polymer raw material]
ADMA: 2-adamantyl methacrylate DCPMA: dicyclopentanyl methacrylate GMA: glycidyl methacrylate 4HBAGE: 4-hydroxybutyl acrylate glycidyl ether MA: methyl acrylate PhMI: N-phenylmaleimide St: styrene AIBN: azobisisobutyro Nitrile [solvent]
CHN: cyclohexanone [(B) component]
GT-401: butanetetracarboxylic acid tetra(3,4-epoxycyclohexylmethyl)-modified ε-caprolactone [Epolead GT-401 (manufactured by Daicel Corporation)]
[(C) component]
SI-B3A: tetrakis pentafluorophenylsulfonium borate salt [San-Aid SI-B3A (manufactured by Sanshin Chemical Industry Co., Ltd.)]

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

(1) Synthesis of component (A) [Synthesis Example 1]
5.00 g (22.70 mmol) of ADMA as a non-crosslinking monomer, 0.17 g (1.19 mmol) of GMA as a crosslinking monomer, and 0.12 g (0.72 mmol) of AIBN as a polymerization catalyst were dissolved in 50.0 g of CHN and heated under reflux. An acrylic copolymer solution was obtained by reacting for 20 hours. The acrylic copolymer solution was gradually added dropwise to 500.0 g of hexane to precipitate a solid, filtered and dried under reduced pressure to obtain an acrylic polymer (PA-1). Mw of the obtained acrylic copolymer was 18,000.

[Synthesis Examples 2 to 8]
Polymers (PA-2) to (PA-8) were obtained in the same manner as in Synthesis Example 1, except that the types and amounts of the raw material compounds were as shown in Table 1 below. Table 1 shows the Mw and Tg of the obtained polymer.

(2) Preparation of resin substrate-forming composition [Preparation Example 1]
10 g of Zeonor (registered trademark) 1020R (a cycloolefin polymer manufactured by Nippon Zeon Co., Ltd.) and 3 g of Epolead (registered trademark) GT401 (manufactured by Daicel Corporation) were added to an eggplant flask containing 100 g of carbon tetrachloride as a solvent. This solution was dissolved by stirring for 24 hours in a nitrogen atmosphere to prepare a resin substrate-forming composition F1.

(3) Preparation of release layer forming composition [Example 1-1]
100 parts by mass of the polymer (PA-1) obtained in Synthesis Example 1 as the component (A) and 1 part by mass of SI-B3A as the component (C) were mixed, and CHN was added thereto to obtain a solid content concentration of 5. A release layer-forming composition (A-1) of 0% by mass was prepared.

[Examples 1-2 to 1-7, Comparative Examples 1-1 to 1-3]
Exfoliation layer-forming compositions (A-2) to (A-10) were prepared in the same manner as in Example 1-1, except that the types and amounts of each component were as shown in Table 2. did.

(3) Production of release layer and resin substrate [Example 2-1]
Using a spin coater (conditions: 2,000 rpm for about 30 seconds), the release layer forming composition (A-1) was coated on a glass substrate (Corning Eagle XG, 100 mm × 100 mm × 0.7 mm) as a substrate. , hereinafter the same). The resulting 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 release layer having a thickness of about 0.1 μm on the glass substrate. , a glass substrate with a release layer was obtained.
After that, using a spin coater (conditions: 200 rpm for about 15 seconds), the resin substrate-forming composition F1 was applied onto the release layer (resin thin film) on the glass substrate. The resulting coating film is heated using a hot plate at 80° C. for 2 minutes, and then heated at 230° C. for 30 minutes using a hot plate to form a resin substrate having a thickness of about 3 μm on the release layer, A glass substrate with a resin substrate and a release layer was obtained.

[Examples 2-2 to 2-7, Comparative Examples 2-1 to 2-3]
Except for using (A-2) to (A-10) as the release layer forming composition, the same operations as in Example 2-1 were carried out, Examples 2-2 to 2-7, Comparative Examples 2-1 to A glass substrate with a resin substrate and a peeling layer of 2-3 was obtained.

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

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

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

Claims (12)

(A) A polymer obtained by using a monomer having an epoxy group (structural unit (a)), wherein the content of the structural unit (a) is 1 to 30 mol% relative to 100 mol% of the total monomer units. A composition for forming a release layer containing a polymer having a glass transition point of 25° C. or higher. (A) The polymer is a polymer obtained using a monomer selected from the group consisting of acrylic acid ester compounds, methacrylic acid ester compounds, maleimide compounds, acrylamide compounds, acrylonitrile, maleic anhydride, styrene compounds and vinyl compounds. The resin composition for forming a release layer according to claim 1. 3. The release layer-forming resin composition according to claim 1, further comprising (B) a cross-linking agent. 4. The resin composition for forming a release layer according to any one of claims 1 to 3, wherein (B) the cross-linking agent is a cross-linking agent having an epoxy group. 5. The release layer-forming resin composition according to any one of claims 1 to 4, further comprising (C) a crosslinking catalyst. 6. The resin composition for forming a release layer according to claim 5, wherein (C) the crosslinking catalyst is a thermal acid generator or a photoacid generator. The release layer-forming resin composition according to any one of claims 3 to 6, wherein the content of (B) the cross-linking agent is 1 to 50 parts by mass with respect to 100 parts by mass of the polymer (A). The release layer-forming resin composition according to any one of claims 5 to 7, wherein the content of (C) the crosslinking catalyst is 0.01 to 20 parts by mass based on 100 parts by mass of the polymer (A). A release layer obtained from the release layer-forming resin composition according to any one of claims 1 to 8. A laminate comprising a release layer according to claim 9 and a resin substrate having a light transmittance of 80% or more at a wavelength of 400 nm. 11. The laminate according to claim 10, wherein the resin substrate is a thermosetting film containing an epoxy compound. a step of applying the composition for forming a release layer according to any one of claims 1 to 8 to a substrate to form a release layer;
Manufacture of a resin substrate, comprising the steps of: forming a resin substrate having a light transmittance of 80% or more at a wavelength of 400 nm on the peeling layer; and peeling the resin substrate with a peeling force of 0.4 N/25 mm or less. Method.