JP4679388B2 - Laminate having releasability and method for producing the same - Google Patents

Description

  The present invention relates to a laminate having releasability (hereinafter simply referred to as a releasable laminate) that is temporarily bonded to the surface of an adhesive layer and used in detail. The present invention relates to a laminate having releasability with stable releasability for pressure-sensitive adhesives, release molding resins, and silicone resin-based pressure-sensitive adhesives.

  In recent years, silicone resin adhesives based on polydimethylsiloxane have excellent heat resistance, cold resistance, water resistance, weather resistance, re-adhesion, electrical insulation, etc. It is widely used as a pressure-sensitive adhesive for various applications because of its excellent adhesion to polyimide, polyamide, polytetrafluoroethylene, silicone rubber, etc. In addition, silicone resin adhesives are not irritating to the skin like acrylic adhesives and are non-toxic, so in recent years they have also been used as medical adhesive tapes such as adhesive bandages. (Patent Literature 1, Patent Literature 2, and Patent Literature 3).

  However, these silicone resin-based pressure-sensitive adhesives have a low surface tension and very strong adhesive force, so that the release properties imparted by a conventional release agent comprising a curable silicone resin are insufficient. If a release paper is attached to the adhesive surface of an adhesive tape or an adhesive label with an adhesive mainly composed of polydimethylsiloxane and stored for a long time before use, the lower layer tape when unrolling from the wound adhesive tape When unwinding while peeling the pressure-sensitive adhesive layer of the tape part unwound from the back side, or when peeling the release paper from the pressure-sensitive adhesive surface, the peeling force increases significantly, sometimes causing breakage between the pressure-sensitive adhesive layers, Or as a label).

Therefore, as a release agent used for a separator for a silicone resin-based adhesive, a (polyfluoro) alkylvinyl monomer, a silane monomer having an ethylenically unsaturated bond and a silicon functional group in the molecule, Copolymer (Patent Document 4), a copolymer of vinylidene fluoride and / or tetrafluoroethylene with another fluorine-containing monomer having an ethylenically unsaturated bond, and a copolymer used in the above publication The composition (patent document 5) containing is disclosed.
Japanese Patent Application Laid-Open No. 07-052326 Japanese Patent Publication No. 07-008554 Japanese Patent Laid-Open No. 03-200885 JP-A-61-228078 Japanese Patent Laid-Open No. 02-281063

  However, the copolymers disclosed in any of these Patent Documents 4 and 5 are also fluorine-based, and are not only expensive themselves, but do not dissolve in ordinary organic solvents such as hydrocarbons. Therefore, it is necessary to apply it after dissolving it in a chlorofluorocarbon solvent, and the chlorofluorocarbon solvent volatilizes and causes destruction of the ozone layer. Therefore, it is desired to use a release agent that dissolves in a normal organic solvent. In addition, the copolymer disclosed in Patent Document 4 has a problem that the adhesiveness and coating film strength to a substrate such as a plastic film are not sufficient, and the release material layer itself is easily peeled off depending on use conditions.

As a result of searching for various mold release components from the above viewpoint, the present inventors have found that a fluoroalkylsilsesquioxane containing one addition polymerizable functional group represented by formula (1) is suitable for a silicone resin adhesive. It was found that the releasability was excellent. However, since this mold release component has insufficient adhesion to the substrate surface such as a plastic film, various investigations have been made on various formulations that improve adhesion without impairing the mold release property of the mold release component. The present invention has arrived at a releasable laminate of the present invention and a method for producing the same which are well adhered to the surface and are useful for general pressure-sensitive adhesives such as acrylic, release molding resins, and silicone resins.

  That is, an object of the present invention is to use a chlorofluorocarbon-based solvent that harms the environment in a release agent solution that is a raw material of a release material layer in a release laminate having a release material layer formed on the surface of a substrate. A silicone resin adhesive that has good adhesion to adherends such as polyimide, polyamide, polytetrafluoroethylene, and silicone rubber, which adheres well to the substrate and is difficult to adhere with ordinary organic adhesives. Providing a laminate paper that has a release property with little release force increase when peeling from the pressure-sensitive adhesive surface even after being applied to the pressure-sensitive adhesive tape used and heat-treated. There is to do.

  The first gist of the present invention is a laminate having releasability formed by forming a release material layer on the surface of a substrate, and the release material layer is a co-polymer having an epoxy resin (A) and a crosslinkable functional group. A copolymer (B) obtained by crosslinking at least two components of the blend (B) in the presence of a curing reaction initiator and having a crosslinkable functional group is a fluorosil represented by the following formula (1). The present invention relates to a laminate having releasability obtained by polymerizing at least two components of sesquioxane (b1) and an addition polymerizable monomer (b2) containing a crosslinkable functional group.

[In Formula (1), one R is an addition-polymerizable functional group, and the other R is independently fluoroalkyl, fluoroarylalkyl or fluoroaryl. ]

  In a preferred embodiment of the invention, in the laminate having releasability, the epoxy resin (A) forming the release material layer contains at least 3,4-epoxycyclohexenylmethyl-3,4-epoxycyclohexenecarboxylate. The total amount of fluorine atoms based on the total mass of the epoxy resin (A) is the total amount of the copolymer (B) having a crosslinkable functional group that is obtained by polymerizing It is a laminate having a releasability at a ratio of 0.01 to 5% by mass.

The second gist of the present invention is that a release agent solution containing at least two components of an epoxy resin (A) and a copolymer (B) having a crosslinkable functional group is applied to the surface of the substrate and baked. A method for producing a laminate having releasability, characterized by forming a release material layer, wherein the copolymer (B) having a crosslinkable functional group is an addition polymerization represented by the formula (1) The present invention relates to a method obtained by polymerizing at least two components of a fluorosilsesquioxane (b1) having a functional functional group and an addition polymerizable monomer (b2) having a crosslinkable functional group.
The preferred form of the present invention is obtained by polymerizing a component in which the epoxy resin (A) forming the release material layer contains at least 3,4-epoxycyclohexenylmethyl-3,4-epoxycyclohexenecarboxylate in the method. The total amount of the copolymer (B) having a crosslinkable functional group that reacts with the polymer is 0.01 to the total amount of fluorine atoms based on the total mass of the epoxy resin (A). This is a method of 5% by mass.

  The laminate having releasability of the present invention uses a copolymer containing a novel silsesquioxane containing a fluorine atom as a release component contained in a release material layer, and this is blended with an existing epoxy resin. By doing so, it does not use an chlorofluorocarbon-based solvent that harms the environment when the release agent solution is applied to the base film, and exhibits excellent release performance by blending a small amount of release components. This is because the copolymer structure, which is the mold release component, has a binding property with the epoxy resin that constitutes the epoxy resin in one region, and it is not theoretically clear in the other region, but is incompatible with the epoxy resin. As a result, it is assumed that the release component is unevenly distributed on the surface of the release material layer. And the obtained release material layer used the silicone adhesive excellent in the adhesiveness with respect to adherends, such as a polyimide, polyamide, polytetrafluoroethylene, and silicone rubber which is difficult to adhere with a general organic adhesive. Even when used for a pressure-sensitive adhesive tape, the peel strength from the pressure-sensitive adhesive layer is stable over time, and the increase in peel strength when peeling from the pressure-sensitive adhesive surface is small even after heat treatment.

  The releasable laminate of the present invention is a laminate having a releasability formed by forming a release material layer on the surface of a substrate, and the release material layer is a copolymer having an epoxy resin (A) and a crosslinkable functional group. The copolymer (B) obtained by crosslinking at least two components of the polymer (B) in the presence of a curing reaction initiator and having a crosslinkable functional group is a fluoropolymer represented by the formula (1). It is obtained by polymerizing at least two components of silsesquioxane (b1) and an addition polymerizable monomer (b2) containing a crosslinkable functional group. Specifically, the releasable laminate of the present invention is, for example, a polymer obtained by polymerizing a component containing at least 3,4-epoxycyclohexenylmethyl-3,4-epoxycyclohexenecarboxylate on the substrate surface. The fluorosilsesquioxane (b1) containing one addition polymerizable functional group and the addition polymerizable monomer (b2) containing a crosslinkable functional group based on the total mass of the epoxy resin (A) A release material layer containing 0.01 to 5% by mass of the copolymer (B) as fluorine atoms is formed.

  The base material is not particularly limited, and in addition to a sheet-like material that is usually used as a base material of a release paper, a packing, a plate-like object, and a container that can be used even when the surface is in contact with a silicone-based adhesive , Tubular bodies, and other amorphous objects. Among them, specific examples of the sheet-like material used as a base material of what is usually referred to as release paper are polyester resins such as polyethylene terephthalate (PET) and polybutylene terephthalate (PBT), polyethylene, polypropylene, and the like. Plastic film such as polyolefin resin, polyvinyl chloride, fluororesin, acrylic resin, polyamide, polycarbonate, polyimide; cellophane, acetate, metal foil, glassine paper, parchment paper with sealing effect, polyethylene, clay binder, polyvinyl alcohol , Starch, carboxymethyl cellulose (CMC), and the like. Among them, a PET film can be preferably cited from the viewpoint of price, waist strength, and the like. It should be noted that other substances such as pigments, dyes, antioxidants, anti-degradation agents, fillers, and UV absorbers are included in the materials constituting these substrates as long as the effects of the present invention are not adversely affected. Further, it may contain an antistatic agent and / or an electromagnetic wave preventing agent. Hereinafter, although it demonstrates centering on what is called said normal release paper, and the method of manufacturing them, it is not limited to these.

  The thickness of the sheet-like material is not particularly limited, but is usually about 10 μm to 2 mm, and is appropriately adjusted depending on the purpose of use as a releasable laminate, but is preferably 15 to 500 μm and practical. Is 20 to 200 μm. For the release material layer forming surface of the above-mentioned base material, use one that has been subjected to easy adhesion treatment such as corona treatment, plasma treatment, blast treatment, etc., and one that has an easy adhesion layer on the surface. Can do. Among these, those subjected to corona treatment are practical.

<Fluorosilsesquioxane (b1) containing addition polymerizable functional group>
The fluorosilsesquioxane (b1) containing the above addition polymerizable functional group (hereinafter simply referred to as fluorosilsesquioxane (b1)) has a silsesquioxane skeleton in its molecular structure. Silsesquioxane is a general term for polysiloxanes represented by [(R—SiO _1.5 ) _n ] (R is an optional substituent). The structure of the silsesquioxane is generally classified into a random structure, a ladder structure, and a cage structure according to the Si—O—Si skeleton. Furthermore, the cage structure is classified into T ₈ , T ₁₀ , T ₁₂ type and the like. Among them, the fluorosilsesquioxane (b1) used in the present invention has a cage structure of T ₈ type [(R—SiO _1.5 ) ₈ ].

The fluorosilsesquioxane (b1) is characterized by having one addition polymerizable functional group. That is, one of R of silsesquioxane [(R—SiO _1.5 ) ₈ ] is an addition polymerizable functional group.

  Examples of the above addition-polymerizable functional groups include groups containing terminal olefin type or internal olefin type radical polymerizable functional groups; groups containing cationic polymerizable functional groups such as vinyl ether and propenyl ether; and vinyl carboxyl and cyanoacryloyl Although a group containing an anion polymerizable functional group such as is included, a radical polymerizable functional group is preferable.

  The radical polymerizable functional group is not particularly limited as long as it is a radical polymerizable group. For example, methacryloyl, acryloyl, allyl, styryl, α-methylstyryl, vinyl, vinyl ether, vinyl ester, acrylamide, methacrylamide, N- Vinylamide, maleic acid ester, fumaric acid ester, N-substituted maleimide and the like are included, and among them, a group containing (meth) acryl or styryl is preferable. Here, (meth) acryl is a general term for acrylic and methacrylic and means acrylic and / or methacrylic. The same shall apply hereinafter.

Examples of the radical polymerizable functional group containing the (meth) acryl include a group represented by the following formula (I). In the formula (I), Y ¹ represents alkylene having 2 to 10 carbon atoms, preferably alkylene having 2 to 6 carbon atoms, more preferably alkylene (propylene) having 3 carbon atoms. X represents hydrogen or alkyl having 1 to 3 carbon atoms, preferably hydrogen or methyl.

Examples of the group radically polymerizable functional group containing styryl include a group represented by the following formula (II). In formula (II), Y ² represents a single bond or alkylene having 1 to 10 carbon atoms, preferably a single bond or alkylene having 1 to 6 carbon atoms, more preferably a single bond or alkylene having 2 carbon atoms (ethylene). Vinyl is bonded to any carbon of the benzene ring, and preferably bonded to carbon in the para position with respect to Y ² .

The fluorosilsesquioxane (b1) is characterized by having fluoroalkyl, fluoroarylalkyl, or fluoroaryl. That is, all the Rs other than the aforementioned addition polymerizable functional group of silsesquioxane (R—SiO _1.5 ) _n are fluoroalkyl, fluoroarylalkyl and / or fluoroaryl.

The fluoroalkyl may be linear or branched. This fluoroalkyl has 1 to 20 carbon atoms, preferably 3 to 14 carbon atoms. Furthermore, any methylene of the fluoroalkyl may be replaced with oxygen. Here, methylene includes —CH ₂ —, —CFH—, or —CF ₂ —. That is, “any methylene may be replaced with oxygen” means that —CH ₂ —, —CFH—, or —CF ₂ — may be replaced with —O—. However, in fluoroalkyl, two oxygens are not bonded (—OO—). That is, the fluoroalkyl may have an ether bond. Also, in the preferred fluoroalkyl, the methylene adjacent to Si is not replaced by oxygen, and the terminal opposite to Si is CF ₃ . Furthermore, it is preferable that —CF ₂ — be replaced with oxygen rather than —CH ₂ — or —CFH— to be replaced with oxygen. Preferred examples of such fluoroalkyl include 3,3,3-trifluoropropyl, 3,3,4,4,4-pentafluorobutyl, 3,3,4,4,5,5,6,6, 6-nonafluorohexyl, tridecafluoro-1,1,2,2-tetrahydrooctyl, heptadecafluoro-1,1,2,2-tetrahydrododecyl, henicosafluoro-1,1,2,2-tetrahydro Dodecyl, pentacosafluoro-1,1,2,2-tetrahydrotetradecyl, (3-heptafluoroisopropoxy) propyl and the like are included. Of these, perfluoroalkylethyl is preferably exemplified.

  The fluoroarylalkyl is an alkyl containing an aryl containing fluorine, and preferably has 7 to 20 carbon atoms, more preferably 7 to 10 carbon atoms. The fluorine contained is preferably one in which any one or more hydrogens in aryl are replaced with fluorine or trifluoromethyl. Examples of the aryl moiety include phenyl, naphthyl and the like, as well as heteroaryl, and examples of the alkyl moiety include methyl, ethyl, propyl and the like.

  The fluoroaryl is one in which any one or two or more hydrogens in the aryl are replaced with fluorine or trifluoromethyl, and the number of carbon atoms is preferably 6 to 20, more preferably Is 6. Examples of such aryl include phenyl, naphthyl and the like, as well as heteroaryl. Specific examples include fluorophenyl such as pentafluorophenyl and trifluoromethylphenyl.

  Of the aforementioned fluoroalkyl, fluoroarylalkyl, or fluoroaryl contained in fluorosilsesquioxane (b1), a preferred group is fluoroalkyl, more preferably perfluoroalkylethyl, and even more preferably 3,3. , 3-trifluoropropyl or 3,3,4,4,5,5,6,6,6-nonafluorohexyl.

As described above, the fluorosilsesquioxane (b1) has a T ₈ type structure, one addition polymerizable functional group, and one or more fluoroalkyl, fluoroarylalkyl and / or Or it has fluoroaryl and is represented by the following structural formula (1-0).

In the above formula (1-0), A ¹ is the aforementioned radical polymerizable functional group, and R _f ^{1 to} R _f ⁷ are each independently the aforementioned fluoroalkyl, fluoroarylalkyl, or fluoroaryl. . R _f ^{1 to} R _f ⁷ may be different groups or all may be the same group.

<Addition polymerizable monomer (b2) containing a crosslinkable functional group>
The addition polymerizable monomer (b2) containing the crosslinkable functional group may be a compound having one or more addition polymerizable double bonds, such as a vinyl compound, a vinylidene compound, and a vinylene compound. More specifically, a (meth) acrylic acid derivative or a styrene derivative is exemplified.

  Examples of the (meth) acrylic acid derivative include (meth) acrylic acid, (meth) acrylic acid ester, (meth) acrylic acid amide, (meth) acrylonitrile, and the like.

Examples of the (meth) acrylic acid derivative of the addition polymerizable monomer (b2) include (meth) acrylates containing a crosslinkable functional group. Examples of such crosslinkable functional groups include epoxies such as glycidyl and epoxycyclohexyl, oxetanyl, isocyanates, acid anhydrides, carboxyls, hydroxyls, etc., preferably epoxies such as glycidyl and oxetanyl. Specific examples of the (meth) acrylate containing the crosslinkable functional group include hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate; glycidyl (meth) acrylate and the like Epoxy-containing (meth) acrylates; alicyclic epoxy-containing (meth) acrylates such as 3,4-epoxycyclohexylmethyl (meth) acrylate; oxetanyl-containing (meta) such as 3-ethyl-3- (meth) acryloyloxymethyloxetane ) Acrylate; 2- (meth) acryloyloxyethyl isocyanate; γ- (methacryloyloxypropyl) trimethoxysilane; (meth) acrylate-2-aminoethyl, 2- (2-bromopropionyloxy) ethyl (meth) acrylate, 2 -(2-bu Moisobutyryloxy) ethyl (meth) acrylate; 1- (meth) acryloxy-2-phenyl-2- (2,2,6,6-tetramethyl-1-piperidinyloxy) ethane, 1- (4 -((4- (meth) acryloxy) ethoxyethyl) phenylethoxy) piperidine, 1,2,2,6,6-pentamethyl-4-piperidyl (meth) acrylate, 2,2,6,6-pentamethyl-4- Piperidyl (meth) acrylate; and the like.

Examples of the styrene derivative having one addition polymerizable double bond include a styrene derivative containing a crosslinkable functional group. Specific examples of such crosslinkable functional groups include epoxies such as glycidyl, oxetanyl, halo, amino, isocyanate, acid anhydride, carboxyl, hydroxyl, thiol, siloxy and the like.
Examples of styrene derivatives containing a crosslinkable functional group include o-aminostyrene, p-styrene chlorosulfonic acid, styrene sulfonic acid and salts thereof, vinylphenylmethyldithiocarbamate, 2- (2-bromopropionyloxy) styrene, 2 -(2-bromoisobutyryloxy) styrene, 1- (2-((4-vinylphenyl) methoxy) -1-phenylethoxy) -2,2,6,6-tetramethylpiperidine and the following formula Are included.

  In addition to the above addition-polymerizable monomer (b2), the addition is carried out as necessary in order to control the mold release performance, compatibility with the epoxy resin, leveling properties, the amount of crosslinkable functional groups in the copolymer, etc. An addition polymerizable monomer other than the polymerizable monomer (b2) can also be used in combination.

The addition polymerizable monomer other than the addition polymerizable monomer (b2) includes a (meth) acrylic acid derivative having one addition polymerizable double bond and a styrene derivative having one addition polymerizable double bond. Is mentioned. Specific examples of such (meth) acrylic acid derivatives include (meth) acrylic acid; methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) ) Acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, n-heptyl (meth) acrylate, n-octyl Alkyl (meth) acrylates such as (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, stearyl (meth) acrylate; phenyl (meth) a Aryl (meth) acrylates such as relate and toluyl (meth) acrylate; arylalkyl (meth) acrylates such as benzyl (meth) acrylate; 2-methoxyethyl (meth) acrylate, 3-methoxypropyl (meth) acrylate, 3-methoxy And alkoxyalkyl (meth) acrylates such as butyl (meth) acrylate; ethylene oxide adducts of (meth) acrylic acid; and the like.

  Specific examples of the (meth) acrylic acid derivative having one addition polymerizable double bond include trifluoromethylmethyl (meth) acrylate, 2-trifluoromethylethyl (meth) acrylate, and 2-perfluoro. Ethylethyl (meth) acrylate, 2-perfluoroethyl-2-perfluorobutylethyl (meth) acrylate, perfluoroethyl (meth) acrylate, trifluoromethyl (meth) acrylate, diperfluoromethylmethyl (meth) acrylate, 2-perfluoromethyl-2-perfluoroethylethyl (meth) acrylate, 2-perfluorohexylethyl (meth) acrylate, 2-perfluorodecylethyl (meth) acrylate, and 2-perfluorohexadecylethyl (meth) Fluoro such as acrylate Such as alkyl (meth) acrylates include.

Further, examples of the (meth) acrylic acid derivative having one addition polymerizable double bond include a (meth) acrylic acid derivative having a silsesquioxane skeleton. Specific examples of such (meth) acrylic acid derivatives having a silsesquioxane skeleton include 3- (3,5,7,9,11,13,15-heptaethylpentacyclo [9.5.1.1 ^{3 , 9.1 5,15} .1 ^7,13 ] ^{octasiloxane-} 1-yl) propyl (meth) acrylate, 3- (3,5,7,9,11,13,15-heptaisobutyl-pentacyclo [9. 5.1.1 ^3,9 .1 ^5,15 .1 ^7,13 ] ^{octasiloxane-} 1-yl) propyl (meth) acrylate, 3- (3,5,7,9,11,13,15-hepta Isooctylpentacyclo [9.5.1.1 ^3,9 .1 ^5,15 .1 ^7,13 ] octasiloxane-1-yl) propyl (meth) acrylate, 3- (3,5,7,9, 11,13,15- hepta cyclopentyl penta cyclo [9.5.1.1 ^3,9 .1 ^5,15 .1 ^7,13] octasiloxane-1-yl) propyl (meth) acrylate Rate, 3- (3,5,7,9,11,13,15- heptaphenyl penta cyclo [9.5.1.1 ^3,9 .1 ^5,15 .1 ^7,13] octasiloxane -1- Yl) propyl (meth) acrylate, 3-[(3,5,7,9,11,13,15-heptaethylpentacyclo [9.5.1.1 ^3,9 .1 ^5,15 .1 ^{7, 13} ] Octasiloxane-1-yloxy) dimethylsilyl] propyl (meth) acrylate, 3-[(3,5,7,9,11,13,15-heptaisobutylpentacyclo [9.5.1.1 ^{3, 9.1 5,15} .1 ^7,13] octasiloxane-1-yloxy) dimethylsilyl] propyl (meth) acrylate, 3 - [(3,5,7,9,11,13,15- hepta isooctyl penta Cyclo [9.5.1.1 ^3,9 .1 ^5,15 .1 ^7,13 ] octasiloxane-1-yloxy) dimethylsilyl] propyl (meth) acrylate Relate, 3-[(3,5,7,9,11,13,15-heptacyclopentylpentacyclo [9.5.1.1 ^3,9 .1 ^5,15 .1 ^7,13 ] octasiloxane-1 -Yloxy) dimethylsilyl] propyl (meth) acrylate, 3-[(3,5,7,9,11,13,15-heptaphenylpentacyclo [9.5.1.1 ^3,9 .1 ^{5,15 .1,7,13} ] octasiloxane-1-yloxy) dimethylsilyl] propyl (meth) acrylate and the like.
An example of a styrene derivative is a styrene derivative having one addition polymerizable double bond. Specific examples of the styrene derivative having one addition polymerizable double bond include styrene, vinyltoluene, α-methylstyrene, p-chlorostyrene; and the like.

Examples of the styrene derivative having one addition polymerizable double bond include a styrene derivative containing silsesquioxane. Examples of styrene derivatives containing such silsesquioxanes include 1- (4-vinylphenyl) -3,5,7,9,11,13,15-heptaethylpentacyclo [9.5.1.1 ^{3, 9} ． 1 ^5,15 . 1 ^7,13 ] octasiloxane, 1- (4-vinylphenyl) -3,5,7,9,11,13,15-heptaisobutylpentacyclo [9.5.1.1 ^3,9 . 1 ^5,15 . 1 ^7,13 ] octasiloxane, 1- (4-vinylphenyl) -3,5,7,9,11,13,15-heptaisooctylpentacyclo [9.5.1.1 ^3,9 . 1 ^5,15 . 1 ^7,13 ] octasiloxane, 1- (4-vinylphenyl) -3,5,7,9,11,13,15-heptacyclopentylpentacyclo [9.5.1.1 ^3,9 . 1 ^5,15 . 1 ^7,13 ] octasiloxane, and 1- (4-vinylphenyl) -3,5,7,9,11,13,15-heptaphenylpentacyclo [9.5.1.1 ^3,9 . 1 ^5,15 . Octasiloxane containing a 4-vinylphenyl group (T ₈ type silsesquioxane), such as 1 ^7,13 ] octasiloxane; and 3- (3,5,7,9,11,13,15-heptaethyl Pentacyclo [9.5.1.1 ^3,9 .1 ^5,15 .1 ^7,13 ] octasiloxane-1-yl) ethylstyrene, 3- (3,5,7,9,11,13,15) -Heptaisobutylpentacyclo [9.5.1.1 ^3,9 .1 ^5,15 .1 ^7,13 ] octasiloxane-1-yl) ethylstyrene, 3- (3,5,7,9,11, 13,15- hepta isooctyl penta cyclo [9.5.1.1 ^3,9 .1 ^5,15 .1 ^7,13] octasiloxane-1-yl) ethyl styrene, 3- (3,5,7, 9,11,13,15-heptacyclopentylpentacyclo [9.5.1.1 ^3,9 .1 ^5,15 .1 ^7,13 ] octaoctasiloxane-1-yl) ethylstyrene, 3- ( 3,5,7,9,11,13,15-heptaphenylpentacyclo [9.5.1.1 ^3,9 .1 ^5,15 .1 ^7,13 ] octasiloxane-1-yl) ethylstyrene, 3-((3,5,7,9,11,13,15-heptaethylpentacyclo [9.5.1.1 ^3,9 .1 ^5,15 .1 ^7,13 ] octasiloxane-1-yloxy ) Dimethylsilyl) ethylstyrene, 3-((3,5,7,9,11,13,15-heptaisobutylpentacyclo [9.5.1.1 ^3,9 .1 ^5,15 .1 ^7,13 ] Octasiloxane-1-yloxy) dimethylsilyl) ethylstyrene, 3-((3,5,7,9,11,13,15-heptaisooctylpentacyclo [9.5.1.1 ^3,9 .1] ^5,15 .1 ^7,13] octasiloxane-1-yloxy) dimethylsilyl) ethylstyrene, 3 - ((3,5,7,9,11,13,15- hepta cyclopentyl point pen Tashi Chlo [9.5.1.1 ^3,9 .1 ^5,15 .1 ^7,13 ] octasiloxane-1-yloxy) dimethylsilyl) ethylstyrene, and 3-((3,5,7,9,11) , 13,15- heptaphenyl penta cyclo [9.5.1.1 ^3,9 .1 ^5,15 .1 ^7,13], such octasiloxane-1-yloxy) dimethylsilyl) ethylstyrene, 4-vinylphenyl Octasiloxane containing an ethyl group (T ₈ type silsesquioxane);

  Furthermore, main chains derived from styrene, (meth) acrylic acid ester, siloxane, and alkylene oxide such as ethylene oxide and propylene oxide as addition polymerizable monomers other than the addition polymerizable monomer (b2). And a macromonomer having one polymerizable double bond.

<Addition polymer>
The copolymer (B) constituting the release material layer of the release laminate of the present invention may be an ordered copolymer such as a block copolymer or a random copolymer. A random copolymer is preferable. Further, the copolymer (B) may have a cross-linked structure or a graft copolymer.

The copolymer (B) comprises at least a structural unit derived from fluorosilsesquioxane (b1) (hereinafter referred to as structural unit (a)) and a structural unit derived from monomer (b) (hereinafter referred to as structural unit ( b)).
The molar ratio of the structural unit (a) to the structural unit (b) in the copolymer (B) is (a) :( b) = 99.999: 0.001 to 0.001: 99.999. However, it is preferable that (a) :( b) = 0.001: 99.999-50: 50 in order to exhibit a sufficient surface modifying ability and to obtain high solubility in a solvent. Moreover, it is preferable that the fluorosilsesquioxane (b1) contained in said copolymer (B) is 0.01-60 mass%.

  The weight average molecular weight of the copolymer (B) varies depending on the content of the structural unit (a), but is 1300 to 1 million as a guide. On the other hand, the molecular weight distribution (Mw / Mn) of the addition copolymer (B) is about 1.01 to 2.5 as a guide.

  Moreover, the ratio of the structural unit derived from the addition polymerizable monomer containing a crosslinkable functional group in the structural unit (b) contained in the copolymer (B) is not particularly limited, and the copolymer ( In order to achieve a good reactivity with the matrix resin monomer in order to achieve binding properties with the epoxy resin (A) which is a matrix resin to be blended when using B) as a coating agent, a crosslinkable functional group is used. It only needs to contain a group.

  The copolymer (B) includes fluorosilsesquioxane (b1), an addition polymerizable monomer (b2) having a crosslinkable functional group, and, if necessary, an addition polymerization having the crosslinkable functional group. It can be obtained by subjecting addition-polymerizable functional groups other than the polymerizable monomer (b2) to a monomer raw material and addition-polymerizing them. When a plurality of types of monomers are used as the addition polymerizable monomer (b2) having a crosslinkable functional group, the ratio of each monomer is appropriately determined according to the characteristics of the target copolymer. That's fine. The proportion of the addition polymerizable monomer (b2) containing a crosslinkable functional group contained in the other addition polymerizable monomer (b2) is also appropriately selected according to the characteristics of the target copolymer. That's fine. In view of simplicity and versatility, radical copolymerization is preferred.

  Said radical copolymerization reaction can be performed using a polymerization initiator. Examples of the polymerization initiator used include 2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (2-butyronitrile), Azo compounds such as dimethyl-2,2′-azobisisobutyrate, 1,1′-azobis (cyclohexane-1-carbonitrile); benzoyl peroxide, lauryl peroxide, octanoyl peroxide, acetyl peroxide, di peroxides such as -t-butyl peroxide, t-butylcumyl peroxide, dicumyl peroxide, t-butyl peroxyacetate, t-butylperoxybenzoate, t-butylperoxyneodecanoate; and tetraethyl Initiators such as dithiocarbamates such as thiuram disulfide;

Furthermore, examples of the radical copolymerization reaction include living radical polymerization and photopolymerization.
The living radical polymerization described above can be performed using a polymerization initiator represented by the following cited documents A to C, represented by atom transfer radical polymerization; reversible addition-fragmentation chain transfer; iodine transfer polymerization; iniferter polymerization. it can.
・ Cited document A: supervised by Mikiharu Tsunoike, Takeshi Endo, radical polymerization handbook, issued August 10, 1999, issued by NTS).
・ Cited document B: HANDBOOK OF RADICAL POLYMERIZATION, K. Matyjaszewski, TP Davis, Eds., John Wiley and Sons, Canada 2002
・ Cited document C: JP-A-2005-105265

Said photopolymerization can be performed using the compound of the cited reference D as a photoinitiator.
・ Cited document D: Photopolymer social gathering, Photosensitive material list book, published on March 31, 1996 by Bunshin Publishing).

Specific examples of the photopolymerization initiator used are not particularly limited as long as they are compounds that generate radicals upon irradiation with ultraviolet rays or visible rays. Examples of the compound used as the photopolymerization initiator (D) include benzophenone, Michler's ketone, 4,4′-bis (diethylamino) benzophenone, xanthone, thioxanthone, isopropylxanthone, 2,4-diethylthioxanthone, 2-ethylanthraquinone, acetophenone, 2-hydroxy-2-methylpropiophenone, 2-hydroxy-2-methyl-4'-isopropylpropiophenone, 1-hydroxycyclohexyl phenyl ketone, isopropyl benzoin ether, isobutyl benzoin ether, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, camphorquinone, benzanthrone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino- 1- ( 4-morpholinophenyl) -butanone-1,4-dimethylaminobenzoic acid ethyl, 4-dimethylaminobenzoic acid isoamyl, 4,4′-di (t-butylperoxycarbonyl) benzophenone, 3,4,4′-tri ( t-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2- (4′-methoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (3 ′ , 4'-Dimethoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (2 ', 4'-dimethoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2 -(2'-Methoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4'-pentyloxystyryl) -4,6-bis (trichloromethyl) -s-triazi 4- [p-N, N-di (ethoxycarbonylmethyl)]-2,6-di (trichloromethyl) -s-triazine, 1,3-bis (trichloromethyl) -5- (2'-chlorophenyl) -s-triazine, 1,3-bis (trichloromethyl) -5- (4'-methoxyphenyl) -s-triazine, 2- (p-dimethylaminostyryl) benzoxazole, 2- (p-dimethylaminostyryl) Benzthiazole, 2-mercaptobenzothiazole, 3,3'-carbonylbis (7-diethylaminocoumarin), 2- (o-chlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-bi Imidazole, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetrakis (4-ethoxycarbonylphenyl) -1,2'-biimidazole, 2,2'-bis (2, 4-dichlorophenyl) -4,4 ', 5,5'-tetra Enyl-1,2'-biimidazole, 2,2'-bis (2,4-dibromophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2' -Bis (2,4,6-trichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 3- (2-methyl-2-dimethylaminopropionyl) carbazole, 3 , 6-Bis (2-methyl-2-morpholinopropionyl) -9-n-dodecylcarbazole, 1-hydroxycyclohexyl phenyl ketone, bis (η ⁵ -2,4-cyclopentadien-1-yl) -bis (2, 6-difluoro-3- (1H-pyrrol-1-yl) -phenyl) titanium, and the like. These compounds may be used alone or in combination of two or more. 3,3 ', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone, 3,3', 4,4'-tetra (t-hexylperoxycarbonyl) benzophenone, 3,3'-di (methoxycarbonyl) -4,4'-di (t-butylperoxycarbonyl) benzophenone, 3,4'-di (methoxycarbonyl) -4,3'-di (t-butylperoxycarbonyl) benzophenone, 4,4'-di (methoxy) Carbonyl) -3,3′-di (t-butylperoxycarbonyl) benzophenone is preferred.

  The amount of the polymerization initiator used in the above addition copolymerization may be 0.01 to 10 mol% with respect to the total number of moles of monomers.

  In the addition copolymerization, a chain transfer agent may be used. The molecular weight can be appropriately controlled by using the chain transfer agent. Examples of such chain transfer agents include thio-β-naphthol, thiophenol, n-butyl mercaptan, ethyl thioglycolate, mercaptoethanol, mercaptoacetic acid, isopropyl mercaptan, t-butyl mercaptan, dodecanethiol, thiomalic acid, pentaerythritol. Mercaptans such as tetra (3-mercaptopropionate) and pentaerythritol tetra (3-mercaptoacetate); disulfides such as diphenyl disulfide, diethyl dithioglycolate and diethyl disulfide; Butyrate, carbon tetrachloride, isopropylbenzene, diethyl ketone, chloroform, ethylbenzene, butyl chloride, s-butyl alcohol, methyl ethyl ketone, methyl isobutyl ketone, chloride Pyrene, methyl chloroform, t-butylbenzene, n-butyl alcohol, isobutyl alcohol, acetic acid, ethyl acetate, acetone, dioxane, ethane tetrachloride, chlorobenzene, methylcyclohexane, t-butyl alcohol, benzene, etc. are included, preferably mercaptan It is kind. In particular, mercaptoacetic acid can lower the molecular weight of the polymer and make the molecular weight distribution uniform. Chain transfer agents can be used alone or in admixture of two or more.

The specific production method of the above copolymer (B) may be the same as the production method of a normal addition polymer, for example, solution polymerization method, emulsion polymerization method, suspension polymerization method, bulk polymerization method, A bulk-suspension polymerization method or a polymerization method using supercritical CO ₂ can be used.

  In the case of the above solution polymerization method, fluorosilsesquioxane (b1) and, if necessary, the monomer (b), a polymerization initiator and a chain transfer agent are dissolved in a suitable solvent. Then, the addition polymerization reaction may be performed by heating or irradiation with light.

  Examples of solvents used in the above polymerization reaction include hydrocarbon solvents (benzene, toluene, etc.), ether solvents (diethyl ether, tetrahydrofuran, diphenyl ether, anisole, dimethoxybenzene, etc.), halogenated hydrocarbon solvents (chlorinated). Methylene, chloroform, chlorobenzene, etc.), ketone solvents (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.), alcohol solvents (methanol, ethanol, propanol, isopropanol, n-butyl alcohol, t-butyl alcohol, etc.), nitrile solvents ( Acetonitrile, propionitrile, benzonitrile, etc.), ester solvents (ethyl acetate, butyl acetate, etc.), carbonate solvents (ethylene carbonate, propylene carbonate, etc.), amide solvents (N, N-dimethylformamide, N, N-dimethylacetamide), hydrochlorofluorocarbon solvents (HCFC-141b, HCFC-225), hydrofluorocarbon (HFCs) solvents (having 2 to 4, 5 and 6 or more carbon atoms) HFCs), perfluorocarbon solvents (perfluoropentane, perfluorohexane), alicyclic hydrofluorocarbon solvents (fluorocyclopentane, fluorocyclobutane), oxygen-containing fluorine solvents (fluoroether, fluoropolyether, fluoroketone, fluoro) Alcohol), aromatic fluorine solvents (α, α, α-trifluorotoluene, hexafluorobenzene), and water. These may be used alone or in combination of two or more.

  The amount of the solvent used may be an amount that makes the monomer concentration 10-80% by mass. The reaction temperature is not particularly limited, and may be 0 to 200 ° C. as a guide, and preferably room temperature to 150 ° C. The polymerization reaction can be performed under reduced pressure, normal pressure, or increased pressure depending on the type of monomer and the type of solvent.

  The polymerization reaction is preferably performed in an inert gas atmosphere such as nitrogen or argon. This is because the generated radicals are inactivated by contact with oxygen to suppress the polymerization rate from decreasing, and a polymer having a molecular weight appropriately controlled is obtained. Further, the polymerization reaction is preferably carried out in a polymerization system from which dissolved oxygen is removed under reduced pressure (after removing dissolved oxygen under reduced pressure, the polymerization reaction may be carried out under reduced pressure as it is).

The polymer obtained in the solution may be purified or isolated by a conventional method, or may be used for forming a coating film as it is.

<Formation of release material layer>
The releasable laminate of the present invention is obtained by applying a release agent solution containing at least two components of an epoxy resin (A) and a copolymer (B) having a crosslinkable functional group to a substrate surface and baking it. It can be manufactured by forming a mold material layer. Here, the copolymer (B) having a crosslinkable functional group is composed of fluorosilsesquioxane (b1) having an addition polymerizable functional group represented by the formula (1) and an addition polymerization having a crosslinkable functional group. It is obtained by polymerizing at least two components of the polymerizable monomer (b2). Specifically, the releasable laminate of the present invention is, for example, an addition polymerization containing fluorosilsesquioxane (b1) and a crosslinkable functional group with respect to the raw material composition forming the epoxy resin (A). By applying a release agent solution containing 0.01 to 5% by mass of the copolymer (B) with the functional monomer (b2) as a fluorine atom on the surface of the substrate and baking it to form a release material layer Can be manufactured.

  As an epoxy resin formed from the composition which forms the said epoxy resin (A), any of an aliphatic epoxy resin and an aromatic epoxy resin may be sufficient. The main monomers forming such an epoxy resin include bisphenol A, bisphenol F, hydroquinone, resorcin, dihydroxynaphthalene, bis (4-hydroxyphenyl) methane, bis (4-hydroxyphenyl) dicyclopentane, 4,4 ′. -Dihydroxybenzophenone, bis (4-hydroxyphenyl) ether, bis (4-hydroxy-3-methylphenyl) ether, bis (3,5-dimethyl-4-hydroxyphenyl) ether, bis (4-hydroxyphenyl) sulfide, Bis (4-hydroxy-3-methylphenyl) sulfide, bis (3,5-dimethyl-4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxy-3-methylphenyl) sulfone, Bis (3,5-dimethyl-4-hydroxyphenyl Sulfone, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxy-3-methylphenyl) cyclohexane, 1,1-bis (3,5-dimethyl-4-hydroxyphenyl) cyclohexane 4,4'-dihydroxybiphenyl-3,3 ', 5,5'-tetramethylbiphenyl, bis (hydroxynaphthyl) methane, and 1,1'-binaphthol, 1,1'-bis (3-t- Butyl-6-methyl-4-hydroxyphenyl) butane and the like.

Furthermore, examples of the epoxy resin to be formed include phenol novolac epoxy resins which are glycidyl etherified products of reaction products with phenols such as phenol, о-cresol, catechol, and aldehydes such as formaldehyde;
Polyglycidyl ether of polyphenols containing trityl skeleton obtained by condensation of phenols such as phenol, cresol, methyl-t-butylphenol and aromatic aldehydes such as hydroxybenzaldehyde;
A polyglycidyl ether of a triphenol skeleton-containing polyphenol novolak which is a reaction product of a trityl skeleton-containing polyphenol and formaldehyde;
Polyglycidyl ethers of polyaralkylphenol resins which are reaction products of phenols such as phenol, o-cresol, catechol and the like with xylylene dichloride and (hydroxymethyl) benzene;
Fat, which is a glycidyl ether of a reaction product of phenols such as phenol, o-cresol, catechol, or naphthols such as hydroxynaphthalene and dihydroxynaphthalene, and unsaturated alicyclic hydrocarbons such as dicyclopentadiene and limonene Cyclic hydrocarbon-containing polyphenol resin type epoxy resin or polynaphthol resin type epoxy resin;
Polyglycidyl ethers of alicyclic hydrogen-containing polyphenol novolac resins or polynaphthol novolak resins which are reaction products of alicyclic hydrocarbon-containing polyphenol resins or polynaphthol resins and formaldehyde;
Glycidyl ether compounds of polyhydric phenols obtained by condensation reaction of phenols and aromatic carbonyl compounds;
Phloroglysin, tris (4-hydroxyphenyl) methane, 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane, 1,3-bis [(4-hydroxyphenyl) methyl] benzene, 1,4-bis [(4-hydroxyphenyl) methyl] polyglycidyl ether of trivalent or higher phenols having benzene or the like as a basic skeleton;
Glycidyl ether compounds derived from cyclic phenols such as calixarene;
p-aminophenol, m-aminophenol, 4-aminometacresol, 6-aminometacresol, 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 3,4 ' -Diaminodiphenyl ether, 1,4-bis (4-aminophenoxy) benzene, 1,4-bis (3-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,3-bis (3 -Aminophenoxy) benzene, 2,2-bis (4-aminophenoxyphenyl) propane, p-phenylenediamine, m-phenylenediamine, 2,4-toluenediamine, 2,6-toluenediamine, p-xylylenediamine, m-xylylenediamine, 1,4-cyclohexanebis (methylamine), 1,3-cyclohexanebis Methylamine), N, amine-based epoxy resins derived from N- diglycidyl aniline;
glycidyl ester compounds derived from aromatic carboxylic acids such as p-oxybenzoic acid, m-oxybenzoic acid, terephthalic acid and isophthalic acid;
A hydantoin-based epoxy compound derived from 5,5-dimethylhydantoin or the like;
2,2-bis (3,4-epoxycyclohexyl) propane, 2,2-bis [4- (2,3-epoxypropyl) cyclohexyl] propane, vinylcyclohexene dioxide, 3,4-epoxycyclohexylmethyl-3, Alicyclic epoxy resins such as 4-epoxycyclohexanecarboxylate;
Examples include aliphatic epoxy resins obtained by oxidizing double bonds in unsaturated hydrocarbon compounds such as polybutadiene.

  The formed epoxy resin may be an alicyclic epoxy resin. Specific examples thereof include a polyglycidyl ether of a polyhydric alcohol having at least one alicyclic ring, or a cyclohexane oxide or cyclopentene oxide-containing compound obtained by epoxidizing a cyclohexene or cyclopentene ring-containing compound with an oxidizing agent. The resulting epoxy resin.

  For example, hydrogenated bisphenol A diglycidyl ether, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy 1-methylcyclohexyl-3,4-epoxy 1-methylcyclohexanecarboxylate, 6 -Methyl-3,4-epoxycyclohexylmethyl-6-methyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy 3-methylcyclohexylmethyl-3,4-epoxy 3-methylcyclohexanecarboxylate, 3,4 -Epoxy 5-methylcyclohexylmethyl-3,4-epoxy 5-methylcyclohexanecarboxylate, 2- (3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy) cyclohexane-metadioxane, bis (3 , 4-Epoxycyclohexylmethyl Adipate, vinylcyclohexene dioxide, 4-vinyl epoxycyclohexane, bis (3,4-epoxy 6-methylcyclohexylmethyl) adipate, 3,4-epoxy 6-methylcyclohexyl carboxylate, methylene bis (3,4-epoxycyclohexane), Dicyclopentadiene diepoxide, ethylene glycol di (3,4-epoxycyclohexylmethyl) ether, ethylene bis (3,4-epoxycyclohexanecarboxylate), dioctyl epoxyhexahydrophthalate, di-2-ethylhexyl epoxyhexahydrophthalate And an epoxy resin obtained from the above.

Furthermore, examples of the epoxy resin to be formed include an epoxy resin obtained from a polyglycidyl ether of an aliphatic polyhydric alcohol or an alkylene oxide adduct thereof; an epoxy resin obtained from a polyglycidyl ester of an aliphatic long-chain polybasic acid Homopolymer synthesized by vinyl polymerization of glycidyl acrylate or glycidyl methacrylate; glycidyl acrylate or copolymers synthesized by vinyl polymerization of glycidyl methacrylate and other vinyl monomers, and the like.

  Specific examples of the polyglycidyl ether include 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, triglycidyl ether of glycerin, triglycidyl ether of trimethylolpropane, tetraglycidyl ether of sorbitol, Examples include diglycidyl ethers of polyhydric alcohols such as hexaglycidyl ether of dipentaerythritol, diglycidyl ether of polyethylene glycol, and diglycidyl ether of polypropylene glycol.

  In addition, specific examples of the polyglycidyl ester include a polyether polyol polyglycidyl obtained by adding one or more alkylene oxides to an aliphatic polyhydric alcohol such as propylene glycol, trimethylolpropane, and glycerin. Ethers, diglycidyl esters of long aliphatic dibasic acids are included.

  Further examples of the epoxy resin formed above are obtained from monoglycidyl ether of aliphatic higher alcohol, monoglycidyl ether of phenol, cresol, butylphenol, or polyether alcohol obtained by adding alkylene oxide to these. Epoxy resins; epoxy resins obtained from glycidyl esters of higher fatty acids; epoxy resins obtained from epoxidized soybean oil, octyl epoxy stearate, butyl epoxy stearate, epoxidized linseed oil, epoxidized polybutadiene, and the like.

  The blending ratio of the epoxy resin (A) and the copolymer (B) to be formed is not particularly limited, but the use of an excessive copolymer (B) is not preferable in terms of cost efficiency. Therefore, from the viewpoint of releasability of the release material layer, the content concentration of the copolymer (B) in the release material layer is preferably blended so as to be 0.01 to 5% by mass as fluorine atoms. It is practical to blend so that it may become 0.01-3 mass% as an atom.

  The release agent solution containing the raw material composition for forming the epoxy resin (A) and the copolymer (B) that is applied to the substrate surface and baked to form the release material layer is usually further subjected to a curing reaction. An initiator is used in combination. There is no restriction | limiting in said hardening reaction initiator, What is necessary is just a compound which can discharge | release the substance which starts cationic polymerization by active energy ray irradiation or a thermal energy. Examples of such curing reaction initiators include carboxylic acids, amines, acid anhydride compounds and acid generators, and preferably double salts or derivatives thereof which are onium salts that release Lewis acids.

Typical examples of the curing reaction initiator include cation and anion salts represented by the following general formula.
[A] ^{m +} [B] ^m-

In the above formula, the cation [A] ^{m +} is preferably an onium ion, and is represented by the following formula, for example.
[(Α) _a Q] ^{m +}

In said formula, (alpha) is a C1-C60 organic group which may contain how many atoms other than a carbon atom. a is an integer of 1-5. The a α's are independent and may be the same or different. Further, at least one α is preferably an organic group having an aromatic ring.
Q is an atom or atomic group selected from the group consisting of S, N, Se, Te, P, As, Sb, Bi, O, I, Br, Cl, F, and N = N. Further, when the valence of Q in the cation [A] ^{m +} is q, m = a−q (where N = N is treated as valence 0).

On the other hand, the anion [B] ^m− is preferably a halide complex, and is represented by the following formula, for example.
[LX _b ] ^m-

  In the above formula, L is a metal or metalloid which is a central atom of a halide complex, and B, P, As, Sb, Fe, Sn, Bi, Al, Ca, In, Ti, Zn, Sc, V, Cr, Mn, Co and the like. X is a halogen atom. b is an integer of 3-7.

Further, when the valence of L in the anion [LX _b ] ^m− is p, m = b−p.

Specific examples of the anion [LX _b ] ^{m− represented by} the above general formula include tetrafluoroborate (BF ₄ ), hexafluorophosphate (PF ₆ ), hexafluoroantimonate (SbF ₆ ), hexafluoroarsenate. (AsF ₆ ), hexachloroantimonate (SbCl ₆ ) and the like are included

As the anion [B] ^m− , those represented by the following formula can also be preferably used. L, X, and b are the same as described above.
[LX _b-1 (OH)] ^m−

Examples of the anion [B] ^m- include perchlorate ion (ClO ₄ ) ⁻ , trifluoromethyl sulfite ion (CF ₃ SO ₃ ) ⁻ , fluorosulfonate ion (FSO ₃ ) ⁻ , and toluenesulfonate anion. Ions, trinitrobenzenesulfonic acid anions, and the like are also included.

Among such onium salts, the curing reaction initiator in the present invention is more preferably an aromatic onium salt exemplified by the following (A) to (C). Among these, one of them can be used alone, or two or more of them can be mixed and used.
(Ii) Phenyldiazonium hexafluorophosphate, aryldiazonium salts such as 4-methoxyphenyldiazonium hexafluoroantimonate, 4-methylphenyldiazonium hexafluorophosphate, (b) diphenyliodonium hexafluoroantimonate, di (4-methylphenyl) iodonium Diaryl iodonium salts such as hexafluorophosphate and di (4-t-butylphenyl) iodonium hexafluorophosphate (c) Triphenylsulfonium hexafluoroantimonate, tris (4-methoxyphenyl) sulfonium hexafluorophosphate, diphenyl-4-thio Phenoxyphenylsulfonium hexafluoroantimonate, diphenyl-4-thiophenoxyphenylsulfonium Xafluorophosphate, 4,4′-bis (diphenylsulfonio) phenyl sulfide-bis-hexafluoroantimonate, 4,4′-bis (diphenylsulfonio) phenyl sulfide-bis-hexafluorophosphate, 4,4 '-Bis [di (β-hydroxyethoxy) phenylsulfonio] phenyl sulfide-bis-hexafluoroantimonate, 4,4'-bis [di (β-hydroxyethoxy) phenylsulfonio] phenyl sulfide-bis-hexafluoro Phosphate, 4- [4 '-(benzoyl) phenylthio] phenyl-di- (4-fluorophenyl) sulfonium hexafluoroantimonate, 4- [4'-(benzoyl) phenylthio] phenyl-di- (4-fluorophenyl) Triaryls such as sulfonium hexafluorophosphate Sulfonium salt

Further, the curing reaction initiator in the present invention may be a mixture of an iron arene complex or an aluminum complex and silanols such as triphenylsilanol.
Examples of iron arene complexes include (η ⁵ -2,4-cyclopentadien-1-yl) [(1,2,3,4,5,6-η)-(1-methylethyl) benzene] -iron. -Hexafluorophosphate and the like, and examples of aluminum complexes include tris (acetylacetonato) aluminum, tris (ethylacetonatoacetato) aluminum, tris (salicylaldehyde) aluminum and the like.

  Among these, from the viewpoint of practical use, the curing reaction initiator in the present invention is preferably an aromatic iodonium salt, an aromatic sulfonium salt, or an iron-arene complex.

  The content of the curing reaction initiator (preferably an acid generator) is preferably 1 mol with respect to 10 to 500 mol of the epoxy group contained in the copolymer (B) and the epoxy resin forming raw material composition.

  The release agent solution used for forming the release material layer of the release laminate of the present invention is prepared by dissolving the raw material composition for forming the epoxy resin (A) and the copolymer (B) in a solvent. And / or dispersed. Although it does not restrict | limit especially as this solvent, It is preferable to contain 20 mass% or more of compounds which have a boiling point of 50 to 200 degreeC. The compound having a boiling point of 50 ° C. to 200 ° C. contained in the solvent may be one kind or a combination of two or more kinds.

  Examples of the compound having a boiling point of 50 ° C. to 200 ° C. include water; alcohols such as methanol, ethanol and isopropyl alcohol; ketones such as methyl ethyl ketone; butyl acetate, butyl propionate, ethyl lactate, methyl oxyacetate, and oxyacetic acid. Ethyl, butyl oxyacetate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-oxypropionate, ethyl 3-oxypropionate, methyl 3-methoxypropionate, 3-methoxy Ethyl propionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, methyl 2-methoxypropionate, 2-methoxypropionate Ethyl ethyl 2-propylpropionate 2-methyl 2-ethoxypropionate 2-ethyl ethyl 2-ethoxypropionate 2-oxy-2-methylpropionate 2-ethyl 2-oxy-2-methylpropionate 2-methoxy -Methyl-2-methylpropionate, 2-ethyl-2-ethoxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate Aliphatic ethers such as dioxane; cyclic ethers such as dioxane; ketones such as cyclohexanone and cyclopentanone; aromatics such as toluene and xylene; cyclic esters such as γ-butyrolactone; N, N-dimethylacetamide and the like.

Furthermore, examples of the compound having a boiling point of 50 ° C. to 200 ° C. include glycol or a derivative thereof. Examples of glycols include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,4-butanediol, and the like.
Examples of the above glycol derivatives include ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, and the like glycol monoethers; propylene glycol monomethyl ether acetate, Propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, etc. Monoether acetate; glycol dimethyl ether such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether; hydrochlorofluorocarbon solvents (HCFC-141b, HCFC-225), hydrofluorocarbon (HFCs) solvents (2 to 4, 5 carbon atoms) And 6 or more HFCs), perfluorocarbon solvents (perfluoropentane, perfluorohexane), alicyclic hydrofluorocarbon solvents (fluorocyclopentane, fluorocyclobutane), oxygen-containing fluorine solvents (fluoroether, fluoropolyether, Fluoroketone, fluoroalcohol), aromatic fluorine solvent (α, α, α-trifluorotoluene, hexafluorobenzene) Zen), and the like.

  As described above, a chlorofluorocarbon organic solvent can be used as the solvent, but in view of environmental considerations, a nonfluorocarbon organic solvent is preferable. In general, for example, two or more kinds of mixed solvents selected from the group including MEK (2-butanone), CHN (cyclohexanone), MMP (methyl 3-methoxypropionate), and IPA (2-propanol) are suitable. Specifically, a mixed solvent of MEK, MMP, and IPA, or a mixed solvent of MEK, CHN, MMP, and IPA can be used. It is preferable that the blending ratio thereof is appropriately adjusted as necessary, such as the type of the epoxy resin, the type of the copolymer (B), and improvement of leveling properties.

  In the above mixed solvent, in order to improve coating uniformity, further, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, diethylene glycol Monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, ethyl lactate and the like are preferably blended. Among these, considering the safety to the human body, preferable examples of the solvent include propylene glycol monomethyl ether acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, diethylene glycol methyl ethyl ether, ethyl lactate and the like. Is preferred.

  In the present invention, the release agent solution contains any components other than the raw material composition for forming an epoxy resin, the copolymer (B), and a curing initiator, as long as it is necessary and does not hinder the present invention. Can be mixed and dissolved. The concentration of the non-volatile component of the release agent solution obtained as described above is not particularly limited, but is usually 1 to 50% by mass, and practically preferably about 5 to 20% by mass.

  The method for applying the release agent solution to the base film is not particularly limited, but spin coating, roll coating, slit coating, dipping, spray coating, gravure coating, reverse coating, There are a rod coating method, a bar coating method, a die coating method, a kiss coating method, a reverse kiss coating method, an air knife coating method, a curtain coating method, and the like.

  The amount of the release agent solution applied is usually 0.1 to 20 μm as the thickness of the release material layer after firing, but is practically about 0.3 to 3 μm.

The firing conditions after the application of the release agent solution are set in consideration of the curing conditions of the epoxy resin (A) and the heat resistance of the substrate, and the firing temperature is usually 120 to 200 ° C., practically 130. ~
180 ° C. The firing time is adjusted depending on the thickness of the release material layer and the firing temperature, and is usually 15 to 120 seconds. For example, when the thickness of the release material layer is 1 μm and the firing temperature is 160 ° C., the firing time is 45 to 45 seconds. 60 seconds is sufficient.

EXAMPLES Hereinafter, although an Example demonstrates this invention further more concretely, this invention is not restrict | limited by a following example.
In this example, the release properties and water / oil repellency properties of the release material layer of the release paper which is a laminate having release properties of the present invention were measured by the following methods.

(Measurement conditions of peel force (N / cm) as a release property)
Using a tensile tester (Strograph V10-C, manufactured by Toyo Seiki Seisakusho Co., Ltd.), the force (N) required for peeling at a 180 ° angle and a peeling speed of 300 mm / min is expressed in tape width (cm). The value was divided (N / cm).
The smaller the peel force measurement value, the less the force can be peeled off from the adhesive or resin surface.

1) Peel strength test (room temperature)
Acrylic resin adhesive tape (Nitto Denko Corporation, No. 31B, tape width 2.5 cm) and silicone resin adhesive tape (Teraoka Seisakusho, No. 646S, tape width) on the surface of the release agent layer of the release paper 2.5 cm) was bonded, and reciprocating pressure was applied once with a 2 kg pressure roller, and the peeling force between the release material layer and the adhesive layer 24 hours after pressure bonding was measured under the above measurement conditions.

2) Peel strength test (130 ° C)
1. Acrylic resin adhesive tape (Nitto Denko, No. 31B, tape width 2.5 cm) and silicone resin adhesive tape (Teraoka Seisakusho, No. 646S, tape width) on the release material layer surface of the release paper. 5 cm) was pasted together, and one reciprocating pressure was applied with a 2 kg pressure roller, and left at room temperature for 30 minutes after the pressure bonding. Next, after adding a heat history for 1 hour in a high temperature chamber set at 130 ° C., the mixture was allowed to cool for 30 minutes, and the peeling force between the release material layer and the adhesive layer was measured under the above measurement conditions.

3) Residual adhesive strength measurement (80 ° C)
Acrylic resin adhesive tape (manufactured by Nitto Denko Corporation, No. 31B, tape width 2.5 cm) is attached to a polyethylene terephthalate film (film thickness: 75 μm, brand name: Lumirror T-60, manufactured by Toray Industries, Inc.), 2 kg The pressure roller was reciprocated once and left at room temperature for 30 minutes after the pressure bonding. Next, after adding a heat history for 30 minutes in a high temperature chamber set at 80 ° C., the mixture was allowed to cool for 30 minutes and again untreated polyethylene terephthalate film (film thickness: 75 μm, brand name: Lumirror T-60, Affixed to Toray Industries, Inc.) and reciprocated with a 2 kg pressure roller. The peel force 30 minutes after the pressure bonding was measured under the above measurement conditions, and was defined as the basic adhesive force (f ₀ ) with the acrylic resin adhesive tape.

Separately, an acrylic resin adhesive tape (manufactured by Nitto Denko Corporation, No. 31B, tape width 2.5 cm) is attached to the release material layer of the release paper, and 1 reciprocating pressure is applied with a 2 kg pressure roller. Left at room temperature for minutes. Next, after adding a heat history for 30 minutes in a high temperature chamber set at 80 ° C., the film was allowed to cool for 30 minutes, and this cooled acrylic resin adhesive tape was again treated with an untreated polyethylene terephthalate film (film thickness). : 75 μm, brand name: Lumirror T-60, manufactured by Toray Industries, Inc.), and reciprocally bonded by a 2 kg pressure roller. The peel force 30 minutes after the pressure bonding was measured under the above measurement conditions, and was defined as the residual adhesive force (f) with the acrylic resin adhesive tape. From the obtained basic adhesive force (f ₀ ) and residual adhesive force (f), the residual adhesive rate (%) was determined using the following formula.
Residual adhesion rate (%) = (f / f ₀ ) × 100

4) Measurement of contact angle and surface free energy Distilled water (for nitrogen / phosphorus measurement, manufactured by Kanto Chemical Co., Inc.) and methylene iodide (99%, Aldrich) are used as probe liquids on the surface of the release material layer cured from the release paper. The surface free energy was calculated from these contact angle values according to Kaelble-Uy theory.

5) Love-off test The cured release layer layer surface of the release paper was reciprocated 10 times with the finger pad, and the presence or absence of the coating film was evaluated.

6) Solvent resistance The hardened release material layer surface of the release paper was reciprocated 10 times with absorbent cotton impregnated with toluene, and the presence or absence of the coating film was evaluated.

7) Mold release material layer migration test to polyethylene terephthalate film Release paper and polyethylene terephthalate film (film thickness: 75 μm, brand name: Lumirror T-60, Toray on stainless steel plate (material: SUS304, size: 130x130x0.5t) 10) alternately. Then, it is sandwiched between stainless plates (material: SUS304, size: 100x100x1.0t) loaded with 1kg weight, and the temperature and humidity chamber (low temperature and temperature and humidity chamber is maintained at 60 ° C and 95% RH. SF23CRA, manufactured by Kato Corporation). After 24 hours, the surface of the polyethylene terephthalate film that had been in contact with the surface of the release material layer was subjected to surface analysis by X-ray photoelectron spectroscopy to evaluate the state of F and Si component migration from the surface of the release material layer.

8) Release material layer component transfer test to acrylic resin adhesive tape Acrylic resin adhesive tape (Nitto Denko Co., Ltd., No. 31B, tape width 2.5 cm) is attached to the release material layer of release paper, 2 kg The pressure roller was reciprocated once and left at room temperature for 30 minutes after the pressure bonding. Next, after adding a heat history for 30 minutes in a high-temperature chamber set at 80 ° C., the mixture was allowed to cool for 30 minutes, and the adhesive layer of the acrylic resin-based adhesive tape that had been allowed to cool was subjected to surface analysis by X-ray photoelectron spectroscopy. And the state of F and Si component migration from the surface of the release material layer was evaluated.

[Example 1]
Copolymer (A1)
Copolymer (A1) containing compound (a-1) (γ-methacryloxypropyl (heptatrifluoropropyl) -T ₈ -silsesquioxane, manufactured by Chisso Corporation) obtained by radical polymerization and glycidyl methacrylate ) (Trade name: XR-D, manufactured by Chisso Corporation) was used as a mold release component. The weight average molecular weight of the copolymer (A1) determined by gel permeation chromatography (GPC) analysis was 39,000 (in terms of polymethyl methacrylate), and the molecular weight distribution index (Mw / Mn) was 1.50. It was. Moreover, the epoxy content calculated | required by < ¹ > H-NMR measurement of the copolymer (A1) was 53.4 mol%. Further, the fluorine concentration of the copolymer (A1) determined by ¹ H-NMR measurement was 19.3 mass%.

In a 100 ml eggplant type flask, 0.3 g of copolymer (A1), 3,4-epoxycyclohexenylmethyl-3,4-epoxycyclohexenecarboxylate (Celoxide 2021P, epoxy equivalent: 31 mol / g, Daicel Chemical Industries, Ltd.) 4.7 g of non-fluorocarbon organic solvent (2-butanone content: 50%, manufactured by Chisso Corporation) was introduced, stirred and dissolved. Furthermore, as a curing agent, a cationic polymerization initiator (antimony hexafluoride aromatic sulfonium salt compound, manufactured by Chisso Corporation) 0.0814 g (Celoxide 2021P / cationic polymerization initiator = 457/1 (mol ratio), epoxy amount: 13.97 mmol ) Was added to obtain a release agent solution.
The fluorine concentration in the resin solid content (10.0% by mass) of the obtained release agent solution was 1.16% by mass.
Here, the “fluorine concentration in the resin solid content” means the ratio of the mass of fluorine contained in the copolymer (A1) to the total mass of the copolymer (A1) and celoxide 2021P. It calculated from the mass ratio of a polymer (A1) and ceroxide 2021P. The obtained release agent solution was coated on a polyethylene terephthalate film (thickness: 75 μm, brand name: Lumirror T-60, manufactured by Toray Industries, Inc.) using a coating rod # 4 (manufactured by RD Specialties). The resulting coating film was cured and baked for 30 seconds in a high temperature chamber at 150 ° C. to obtain a transparent release paper having a release material layer having a thickness of 0.9 μm. With respect to the obtained release paper, the release performance and the coating film strength of the release material layer were evaluated based on the above evaluation method, and the results are shown in Table 1 together with the main constituent requirements of the release material layer.

  Furthermore, using the obtained release paper, a release material layer component transfer test to a polyethylene terephthalate film and an acrylic resin-based adhesive tape was evaluated based on the above evaluation method, and the results are shown in FIG.

[Comparative Example 1]
Copolymer (B1)
Copolymer containing compound (b-1) ((2-perfluorobutyl) ethyl methacrylate (M-1420, manufactured by Daikin Industries, Ltd.)) represented by the following formula and glycidyl methacrylate, obtained by radical polymerization method (B1) (trade name: XR-DS01, manufactured by Chisso Corporation) was used as a mold release component. The weight average molecular weight of the copolymer (B1) determined by gel permeation chromatography (GPC) analysis was 39,000 (in terms of polymethyl methacrylate), and the molecular weight distribution index (Mw / Mn) was 1.50. It was. Moreover, the epoxy content calculated | required by < ¹ > H-NMR measurement of the copolymer (B1) was 38.9 mol%. Further, the fluorine concentration of the copolymer (B1) determined by ¹ H-NMR measurement was 25.7% by mass.

  In a 100 ml eggplant type flask, 0.3 g of the above copolymer (B1), 3,4-epoxycyclohexenylmethyl-3,4-epoxycyclohexenecarboxylate (Celoxide 2021P, epoxy equivalent: 31 mol / g, Daicel Chemical Industries, Ltd.) 4.7 g of non-fluorocarbon organic solvent (2-butanone content: 50%, manufactured by Chisso Co., Ltd.) was introduced and stirred and dissolved. Furthermore, as a curing agent, a cationic polymerization initiator (antimony hexafluoride aromatic sulfonium salt compound, manufactured by Chisso Corporation) 0.0814 g (Celoxide 2021P / cationic polymerization initiator = 457/1 (molar ratio), epoxy amount: 13.97 mmol ) Was added to obtain a release agent solution.

The fluorine concentration in the resin solid content (10.0% by mass) of the obtained release agent solution was 1.54% by mass.
Here, the “fluorine concentration in the resin solid content” means the ratio of the mass of fluorine contained in the copolymer (B1) to the total mass of the copolymer (B1) and ceroxide 2021P. It calculated from the mass ratio of a polymer (B1) and ceroxide 2021P. The obtained release agent solution was coated on a polyethylene terephthalate film (thickness: 75 μm, brand name: Lumirror T-60, manufactured by Toray Industries, Inc.) using a coating rod # 4 (manufactured by RD Specialties). The resulting coating film was cured and baked for 30 seconds in a high temperature chamber at 150 ° C. to obtain a transparent release paper having a release material layer having a thickness of 0.9 μm. With respect to the obtained release paper, the release characteristics and coating film strength of the release material layer were evaluated based on the evaluation method described above, and the results are shown in Table 1 together with the main constituent requirements of the release material layer.

  Further, using the obtained release paper, a release material layer component transfer test to a polyethylene terephthalate film and an acrylic resin-based adhesive tape was evaluated based on the above evaluation method, and the results are shown in FIG.

[Comparative Example 2]
A platinum-based catalyst (trade name: CAT-PL-50T, manufactured by Shin-Etsu Chemical Co., Ltd.) is added to 100 parts by mass of a fluorosilicone mold release agent (trade name: X-70-201, manufactured by Shin-Etsu Chemical Co., Ltd.). Add 0.5 parts, release agent solution diluted with 400 parts of FR thinner (CFC solvent, manufactured by Shin-Etsu Chemical Co., Ltd.) using coating rod # 3 (manufactured by RD Specialties), polyethylene terephthalate The film was applied on a film (thickness: 100 μm, brand name: Lumirror T-60, manufactured by Toray Industries, Inc.). The obtained coating film was cured and baked in a high temperature chamber at 180 ° C. for 30 seconds to obtain a transparent release paper having a release material layer having a thickness of 0.2 μm. With respect to the obtained release paper, the release characteristics and coating film strength of the release material layer were evaluated based on the evaluation method described above, and the results are shown in Table 1 together with the main constituent requirements of the release material layer. In addition, when said mold release agent X-70-201 was diluted with 2-butanone, toluene, ethyl acetate etc. which are general purpose solvents, it became white gel form and the mold release agent solution which can be applied was not obtained. .

[Comparative Example 3]
Evaluation of release characteristics and coating strength of release material layer based on the above evaluation methods for commercially available general-purpose curable silicone resin-based separate films (Tosero Separator SP-PET-01-25Bu, manufactured by Tosero Co., Ltd.) The results are shown in Table 1.

(Consideration of evaluation results of examples)
When Example 1 and Comparative Example 1 were compared, Example 1 containing a fluoroalkylsilsesquioxane compound had a higher fluorine concentration in the coating film than that of Comparative Example 1, but was separated. It can be seen that the mold characteristics are excellent, and particularly after the heating with the acrylic pressure-sensitive adhesive tape, the mold release characteristics are remarkably excellent after the room temperature and the heating with respect to the silicone pressure-sensitive adhesive tape. Moreover, when Example 1 and Comparative Example 2 are compared, Comparative Example 2 is almost the same level as Example 1 in terms of peel force, but in Example 1, it can be used diluted with 2-butanone, which is a general-purpose solvent. On the other hand, it can be seen that Comparative Example 2 cannot be arbitrarily diluted unless it is an environmentally undesirable fluorocarbon solvent, and further, the strength of the cured coating film is also inferior. About the release material layer component transfer test to polyethylene terephthalate film or acrylic resin-based adhesive tape, as is clear from XPS survey scan spectrum, not only Si but also F component transfer was remarkably observed. Depending on the case, use may not be preferable. Next, when Example 1 and Comparative Example 3 are compared, the separator using the curable silicone resin is inferior to the silicone-based adhesive in releasability and further inferior in the strength of the cured coating film, so that it may be used depending on the application. It turns out that it may be difficult.

  The laminate having releasability of the present invention uses a novel silsesquioxane containing a fluorine atom as a release component, and is well adhered to the substrate by blending an epoxy resin (A) therein. The release agent solution does not use an chlorofluorocarbon solvent that harms the environment, exhibits excellent release properties even when the release component is small in terms of fluorine atom, and is difficult to stick with ordinary organic adhesives. When used as a release paper for pressure-sensitive adhesive tapes using silicone adhesives with excellent adhesion to polyimide, polyamide, polytetrafluoroethylene, silicone rubber, etc. The increase in peeling force at the time is small, the releasability is stable, and the migration of Si and F components from the release material layer is extremely small, so the industrial effect is great.

The figure which shows the result of the mold release material layer component transfer test to the polyethylene terephthalate film of the release paper of Example 1, and an acrylic resin adhesive tape. The figure which shows the result of the mold release material layer component transfer test to the polyethylene terephthalate film of the release paper of the comparative example 1, and an acrylic resin adhesive tape.

Claims (6)

A laminate having a releasability formed by forming a release material layer on a substrate surface, wherein the release material layer comprises at least two components of an epoxy resin (A) and a copolymer having a crosslinkable functional group (B). The copolymer (B) obtained by crosslinking in the presence of a curing reaction initiator and having a crosslinkable functional group is crosslinkable with the fluorosilsesquioxane (b1) represented by the following formula (1). A laminate having releasability obtained by polymerizing at least two components of an addition polymerizable monomer (b2) containing a functional group.

[In Formula (1), one R is an addition-polymerizable functional group, and the other R is independently fluoroalkyl, fluoroarylalkyl or fluoroaryl. ] The laminate having releasability according to claim 1, wherein the fluorosilsesquioxane (b1) having an addition polymerizable functional group is a compound represented by the following formula (1-0).

[In the formula (1-0), A ¹ is an radically polymerizable functional group; R _f ¹ ~R _f ⁷ are each independently any methylene 1 carbon atoms, which may be replaced by oxygen 20 fluoroalkyl, aryl having 6 to 20 carbon atoms in which at least one hydrogen is replaced with fluorine or trifluoromethyl, or 7 to 20 carbon atoms in which at least one hydrogen of aryl is replaced with fluorine or trifluoromethyl Arylalkyl. ] The epoxy resin (A) forming the release material layer is a polymer obtained by polymerizing a component containing at least 3,4-epoxycyclohexenylmethyl-3,4-epoxycyclohexenecarboxylate, and crosslinks reacting therewith The total amount of the copolymer (B) having a functional functional group is a ratio of 0.01 to 5 mass% in terms of the total amount of fluorine atoms based on the total mass of the epoxy resin (A). A laminate having the described releasability. A release agent solution containing at least two components of an epoxy resin (A) and a copolymer (B) having a crosslinkable functional group is applied to a substrate surface and baked to form a release material layer. A method for producing a laminate having releasability, wherein a copolymer having a crosslinkable functional group (B
) Polymerizes at least two components of a fluorosilsesquioxane (b1) having an addition polymerizable functional group represented by the following formula (1) and an addition polymerizable monomer (b2) having a crosslinkable functional group. A method characterized by being obtained.

[In the formula (1), one R is an addition polymerizable functional group, and the other R is independently fluoroalkyl, fluoroarylalkyl or fluoroaryl. ] The method for producing a laminate having releasability according to claim 4, wherein the fluorosilsesquioxane (b1) having an addition polymerizable functional group is a compound represented by the following formula (1-0).

[In Formula (1-0),
A ¹ is a radically polymerizable functional group;
R _f ^{1 to} R _f ⁷ are each independently a fluoroalkyl having 1 to 20 carbon atoms in which any methylene may be replaced with oxygen, and the number of carbons in which at least one hydrogen is replaced with fluorine or trifluoromethyl. 6-20 aryl, or arylalkyl having 7-20 carbons, wherein at least one hydrogen of aryl is replaced by fluorine or trifluoromethyl. ] The epoxy resin (A) forming the release material layer is a polymer obtained by polymerizing a component containing at least 3,4-epoxycyclohexenylmethyl-3,4-epoxycyclohexenecarboxylate, and crosslinks reacting therewith The total amount of the copolymer (B) having a functional functional group is a ratio of 0.01 to 5 mass% in terms of the total amount of fluorine atoms based on the total mass of the epoxy resin (A). The manufacturing method of the laminated body which has the release property of description.

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