JP2019093686A - Release film for transfer film and transfer film - Google Patents

Abstract

To provide a release film for transfer film having good coating property and release property of a transfer layer containing at least one selected from the group consisting of an epoxy compound and a compound having an ethylenically unsaturated group in the molecule.SOLUTION: A release film for transfer film is used for a transfer film on which a transfer layer containing at least one selected from the group consisting of an epoxy compound and a compound having an ethylenically unsaturated group in the molecule is laminated, and has a release layer containing a silicone-modified alkyd resin on a base material film.SELECTED DRAWING: None

Description

  The present invention relates to a release film and a transfer film used for a transfer film on which a transfer layer such as an adhesive layer or a hard coat layer is laminated.

  There is known a transfer film in which a transfer layer is laminated on a release film.

  For example, an adhesive tape or an adhesive sheet (transfer film) in which an epoxy adhesive is laminated on a separator (releasing film) is known (for example, Patent Documents 1 and 2). It is known that an epoxy-based adhesive can be used as a sealing resin of a circuit board or an interlayer insulating resin of a multilayer printed wiring board.

  Moreover, the transfer foil (transfer film) which has a mold release layer and a hard-coat layer in this order on a base material is proposed (for example, patent documents 3, 4). The hard coat layer is made of a cured product of an active energy ray-curable composition containing a polymerizable compound such as urethane (meth) acrylate or polyester (meth) acrylate.

  Moreover, the transfer film in which the antifouling | stain-resistant cured layer was laminated | stacked on the base film is proposed (for example, patent document 5). The antifouling cured layer contains a fluorine-containing polymerizable monomer.

  Further, a transfer material (transfer film) in which an antireflective layer is laminated on a support film having releasability has been proposed (for example, Patent Document 6). The antireflective layer contains a fluorine-containing (meth) acrylate compound and hollow silica.

JP 2005-39247 A JP, 2010-109383, A JP, 2013-185078, A JP, 2017-65017, A International Publication No. 2011/0043361 JP, 2008-151930, A

  The transfer layer in the transfer film described above, that is, the epoxy-based adhesive layer, the hard coat layer, the antifouling layer, the antireflective layer is an epoxy compound or a (meth) acrylate compound (compound having an ethylenically unsaturated group in the molecule) It forms by apply | coating the thermosetting composition or active energy ray curable composition which contains the above on a release film. At this time, the coating property which can apply | coat the said composition uniformly on a release film is calculated | required.

  Moreover, when transcribing the transfer layer of a transfer film to a to-be-adhered body, the releasability which can peel a release film comparatively easily (smoothly) is calculated | required.

  In general, the coatability of the transfer layer onto the release film and the releasability are opposite properties, and the prior art described in the above-mentioned Patent Documents 1 to 6 can fully satisfy the coatability and the releasability simultaneously. It was not a thing.

  Therefore, an object of the present invention is to provide a release film for transfer film having good coatability and releasability of a transfer layer containing at least one selected from the group consisting of epoxy compounds and compounds having an ethylenically unsaturated group in the molecule. To provide. Another object of the present invention is to provide a transfer film provided on the release film of the present invention with at least one selected from the group consisting of an epoxy compound and a compound having an ethylenically unsaturated group in the molecule. It is to provide.

The above object of the present invention is achieved by the following invention.
[1] A release film for use in a transfer film comprising a transfer layer containing at least one member selected from the group consisting of an epoxy compound and a compound having an ethylenically unsaturated group in the molecule, which is a substrate film A release film for transfer film, comprising a release layer containing a silicone-modified alkyd resin.
[2] The release film for transfer film according to [1], wherein the transfer layer is at least one layer selected from the group consisting of an adhesive layer, a hard coat layer, an antifouling layer and an antireflective layer.
[3] The release for transfer film according to [1] or [2], wherein the content of the silicone-modified alkyd resin in the release layer is 40% by mass or more based on 100% by mass of the total solid content of the release layer. Mold film.
[4] The release film for transfer film according to any one of [1] to [3], wherein the release layer further contains a melamine crosslinking agent.
[5] The release film for transfer film according to any one of [1] to [4], wherein an anchor layer is disposed between the base film and the release layer.
[6] The release film for transfer film according to [5], wherein the anchor layer contains a silane compound and a metal complex having an organic ligand.
[7] The release film for transfer film according to [6], wherein the central metal of the metal complex having an organic ligand is at least one selected from the group consisting of aluminum, titanium and zirconium.
[8] [1] to [7] on the release layer of the release film for transfer film, at least one selected from the group consisting of an epoxy compound and a compound having an ethylenically unsaturated group in the molecule A transfer film in which a transfer layer containing one type is laminated.
[9] The transfer film according to [8], wherein the transfer layer is at least one layer selected from the group consisting of an adhesive layer, a hard coat layer, an antifouling layer and an antireflective layer.

  The release film for transfer film of the present invention is excellent in the coatability of the transfer layer containing at least one selected from the group consisting of an epoxy compound and a compound having an ethylenically unsaturated group in the molecule. A transfer layer which is uniform and has a good appearance can be obtained. In addition, since the release film for transfer film of the present invention has good releasability from the transfer layer, it can be relatively easily (smoothly) peeled off when the transfer layer is transferred to the adherend.

  The transfer film in which the transfer layer is laminated on the release film for transfer film of the present invention is a release film having a uniform transfer layer and good appearance and transferring the transfer layer to an adherend. Peelability is good.

  The release film for transfer film of the present invention is a release film for transferring a transfer layer of a transfer film, in which the transfer layer is temporarily laminated on the release film, to an adherend. That is, it is a release film for transfer film used for the transfer film on which the transfer layer is laminated. Hereinafter, the release film for transfer films may only be called "release film."

  The release film of the present invention comprises a release layer containing a silicone-modified alkyd resin on a base film. A transfer layer containing at least one selected from the group consisting of an epoxy compound and a compound having an ethylenically unsaturated group in the molecule is laminated on the release layer of the release film to obtain a transfer film. The transfer layer of this transfer film is brought into contact with the adherend directly or through an adhesive layer etc., and heat and pressure are applied as required, and then the release film is peeled off to transfer the transfer layer to the adherend Transfer-deposited. In the present invention, “containing at least one selected from the group consisting of epoxy compounds and compounds having an ethylenically unsaturated group in the molecule” means epoxy compounds and / or ethylenically unsaturated groups in the molecule. Not only when the compound itself is contained, but also the structure in which the epoxy ring of the epoxy compound is opened and / or the ethylenically unsaturated group of the compound having an ethylenically unsaturated group in the molecule is polymerized to form a single bond It also includes the case of having a structure.

  The release layer of the release film of the present invention is a coated film because the coatability of the transfer layer containing at least one selected from the group consisting of epoxy compounds and compounds having an ethylenically unsaturated group in the molecule is good. A transfer layer which is uniform and has a good appearance can be obtained. Moreover, since the release layer of the release film of the present invention has good releasability from the transfer layer, the release film can be peeled off smoothly after the transfer layer is in close contact with the adherend.

  The adherend to which the transfer layer of the transfer film of the present invention is transferred is not particularly limited, and examples thereof include circuit boards, multilayer printed wiring boards, and plastic resin molded articles. Examples of plastic resin molded products include electronic device housings (portable personal computers, mobile devices, mobile phones, electronic organizers, etc.), home appliances (TVs, refrigerators, washing machines, rice cookers, etc.), suitcases, plastic lenses, Automobile interior members (instrument panels, consourcing boxes, door trims, etc.) and the like can be mentioned.

[Release layer]
The release layer contains a silicone modified alkyd resin.

  In the present invention, the alkyd resin refers to a resin obtained by further reacting a fatty oil or a fatty acid with a chemical structure having a condensation product of a polyhydric alcohol and a polybasic acid as a skeleton.

  Examples of the polyhydric alcohol include dihydric alcohols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, trimethylene glycol, tetramethylene glycol, neopentyl glycol, etc., glycerin, trimethylolethane, trimethylolpropane and the like. And alcohols having a valence of 4 or more such as dihydric alcohol, diglycerin, triglycerin, pentaerythritol, dipentaerythritol, mannitol, sorbit and the like. One of these may be used alone, or two or more of these may be used in combination.

  Examples of the polybasic acid include saturated polybasic acids such as phthalic anhydride, terephthalic acid, succinic acid, adipic acid and sebacic acid, and maleic acid, maleic anhydride, fumaric acid, itaconic acid, citraconic anhydride and the like. Other polybasic acids such as unsaturated polybasic acids, cyclopentadiene-maleic anhydride adducts, terpene-maleic anhydride adducts, rosin-maleic anhydride adducts and the like can be mentioned. One of these may be used alone, or two or more of these may be used in combination.

  As the above-mentioned fatty oil and fatty acid, fatty oil such as soybean oil, linseed oil, tung oil, castor oil, dehydrated castor oil, coconut oil etc. Examples thereof include oils and fats such as stearic acid, ricinoleic acid and dehydrated ricinoleic acid, and fatty acids and the like. One of these may be used alone, or two or more of these may be used in combination.

  As a silicone modifier for obtaining a silicone modified alkyd resin, a compound having an alkoxysilyl group or a silanol group can be used. Specifically, an organopolysiloxane having an organic group such as dimethylpolysiloxane is mentioned, and a part of the organic group is substituted with a phenyl group, an ethyl group, an isopropyl group, a hexyl group, a cyclohexyl group, a hydroxyl group, a vinyl group, etc. It may be done. One of these may be used alone, or two or more of these may be used in combination.

  The silicone modification ratio in the silicone modified alkyd resin is preferably 1 to 30% by mass with respect to 100% by mass of the silicone modified alkyd resin solid content, from the viewpoint of expressing the good coatability and the good releasability of the transfer layer. 10 mass% is more preferable, and 2 to 5 mass% is particularly preferable.

  Silicone modified alkyd resins are commercially available and they can be used. Commercially available products include Shin-Etsu Chemical Co., Ltd. trade names KS-881, KS-882, KS-883, X-62-9022, X-62-9027, X-62-950A, Toray Dow Corning (stock Trade names SR2107 and SR2114, trade name TSR180 manufactured by Toshiba Silicone Co., Ltd., trade names Tesfine 309 and 319 traded by Hitachi Chemical Co., Ltd., and TA31-209E.

  The release layer preferably further contains a crosslinking agent. When the release layer contains a crosslinking agent, the coatability and the releasability of the transfer layer are further improved.

  As a crosslinking agent, an epoxy crosslinking agent, an isocyanate crosslinking agent, an oxazoline crosslinking agent, a carbodiimide crosslinking agent, a melamine crosslinking agent etc. are mentioned, for example. One of these may be used alone, or two or more of these may be used in combination.

  Among the above, melamine crosslinking agents are particularly preferred. The use of a melamine crosslinker further improves the coatability and the releasability.

  As an epoxy crosslinking agent, ethylene glycol diglycidyl ether, glycerol polyglycidyl ether, polybutadiene diglycidyl ether etc. are mentioned, for example.

  As an isocyanate crosslinking agent, hexamethylene diisocyanate, isophorone diisocyanate, tolylene diisocyanate, methylene diphenyl diisocyanate etc. are mentioned, for example.

  As an oxazoline crosslinking agent, for example, 2,2'-bis (2-oxazoline), 2,2'-ethylene-bis (4,4'-dimethyl-2-oxazoline), 2,2'-p-phenylene- The compound which has oxazoline groups, such as a bis (2-oxazoline) and a bis (2- oxazolinyl cyclohexane) sulfide, and an oxazoline group containing polymer are mentioned.

  Examples of carbodiimide crosslinking agents include carbodiimides such as p-phenylene-bis (2,6-xylcarbodiimide), tetramethylene-bis (t-butylcarbodiimide), cyclohexane-1,4-bis (methylene-t-butylcarbodiimide), etc. The compound which has group, and polycarbodiimide which is a polymer which has carbodiimide group are mentioned.

  The melamine compound used as a melamine crosslinking agent is variously used as the amino group of so-called melamine [1,3,5-triazine-2,4,6-triamine] in which amino groups are respectively bonded to three carbon atoms of a triazine ring It is a generic term of the compound which gave the modification | denaturation of, and the thing in which multiple triazine rings were condensed is also included. As the type of modification, a methylolated melamine compound in which at least one of hydrogen atoms of three amino groups is methylolated is preferable, and further, the methylol group of the methylolated melamine compound is partially or lower alcohol having a carbon number of 1 to 4 Preferred are fully etherified alkyl etherified melamine compounds.

  Examples of the alcohol used for the etherification include methyl alcohol, ethyl alcohol, propyl alcohol and butyl alcohol.

  A commercial item can be used for a melamine crosslinking agent. As a commercial item, for example, "Super Beckcamine (registered trademark)" J-820-60, J-821-60, J-1090-65, J-110-60, and J of DIC Corporation. -117-60, J-127-60, J-166-60B, J-105-60, G840, G821, Mitsui Chemicals, Inc. "Yuvan (registered trademark)" 20SB, 20SE60, 20SE60, 21R, 22R, 122, 125, 128, 220, 225, 228, 28-60, 2020, 60R, 62, 62E, 360, 165, 166- 60, No. 169, No. 2061, Sumitomo Chemical Co., Ltd. "Sumimar (registered trademark)" M-100, M-40S, M-55, M-66B, "Cymel (registered trademark) of Nippon Cytech Industries" " 03, 325, 327, 350, 370, 235, 202, 238, 254, 272, 1130, "Nikarak (registered trademark)" MS17, MX15 of Sanwa Chemical Co., Ltd. MX430 and MX600, Harma Chemical Co., Ltd. Bangsemin SM-975, and Hara Kasei Co., Ltd. SM-960, and Hitachi Chemical Co., Ltd. "MELAN (registered trademark)" 265 and 2650 L.

  Among the commercially available products of the silicone-modified alkyd resin described above, those containing a melamine crosslinking agent or the like as a crosslinking agent for curing the silicone-modified alkyd resin are present. When such a commercially available product is used, it is not always necessary to newly add the above-mentioned crosslinking agent, but the addition is not hindered.

  The release layer preferably contains an acid catalyst in order to accelerate the curing of the release layer. As the acid catalyst, sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, p-toluenesulfonic acid and the like can be mentioned. Among these, p-toluenesulfonic acid is preferably used.

  The content of the silicone-modified alkyd resin in the release layer is preferably 40% by mass or more based on 100% by mass of the total solid content of the release layer from the viewpoint of improving the coatability and releasability of the transfer layer. 50 mass% or more is more preferable, and 60 mass% or more is especially preferable. On the other hand, if the content of the silicone-modified alkyd resin is too large, the strength (hardness) of the release layer may be reduced and the solvent resistance and the heat resistance may be reduced. % By mass or less is preferable, 95% by mass or less is more preferable, and 90% by mass or less is particularly preferable.

  The content of the crosslinking agent in the case where the release layer contains a crosslinking agent is 3% by mass or more based on 100% by mass of the solid content of the release layer from the viewpoint of improving the coatability and releasability of the transfer layer. Is preferable, 5 mass% or more is more preferable, and 10 mass% or more is particularly preferable. On the other hand, when the content of the crosslinking agent is too large, the releasability may be reduced, so the content of the crosslinking agent is preferably 60% by mass or less, more preferably 50% by mass or less, and 40% by mass or less Particularly preferred.

  The content of the acid catalyst when the release layer contains an acid catalyst is 0.1 to 10 mass based on 100% by mass of the total solid content of the release layer from the viewpoint of improving the coatability and the releasability. % Is preferable, 0.3-5 mass% is more preferable, 0.5-3 mass% is especially preferable.

  The release layer can further contain a binder resin. As such binder resin, polyurethane resin, acrylic resin, polyester resin and the like can be mentioned.

  The release layer is preferably formed by applying a composition containing a silicone modified alkyd resin on a substrate film and heat curing. That is, the composition for forming the release layer is preferably a thermosetting composition. The composition preferably contains a silicone-modified alkyd resin and a crosslinking agent, and more preferably contains an acid catalyst. The composition can also contain a binder resin.

  The conditions (heating temperature and time) for curing the composition are not particularly limited, but the heating temperature is preferably 70 ° C. or more, more preferably 100 ° C. or more, and particularly preferably 150 ° C. or more. The upper limit is about 300 ° C. The heating time is preferably 3 to 300 seconds, more preferably 5 to 200 seconds.

  The composition can be applied by, for example, a wet coating method. Examples of the wet coating method include reverse coating method, spray coating method, bar coating method, gravure coating method, rod coating method, die coating method, spin coating method, extrusion coating method, curtain coating method and the like.

  30-1000 nm is preferable, 50-600 nm is more preferable, 70-500 nm is further more preferable, and, as for the thickness of a release layer, 100-400 nm is especially preferable.

20-35 mJ / m < ² > is preferable, as for the surface free energy of a release layer, 21-32 mJ / m < ² > is more preferable, and 22-30 mJ / m < ² > is especially preferable. When the surface free energy of the release layer is in the above range, the coatability and the releasability of the transfer layer are further improved.

  The release layer containing the silicone-modified alkyd resin can adjust the surface free energy to the above range, and the surface free energy can be easily adjusted to the above range by further containing a crosslinking agent.

  Here, the surface free energy can be measured using a contact angle meter, for example, “Drop Master DM 501” manufactured by Kyowa Interface Science Co., Ltd. Details will be described later.

  The surface state of the release layer is preferably relatively smooth from the viewpoint of improving the coatability and the releasability of the transfer layer. Specifically, the surface roughness SRa of the release layer is preferably 50 nm or less, more preferably 30 nm or less, and particularly preferably 15 nm or less. The surface roughness SRa is preferably 1 nm or more, more preferably 3 nm or more, and particularly preferably 5 nm or more, from the viewpoint of securing the slipperiness and winding of the release film and the transfer film.

  As a method of controlling the surface roughness SRa of the release layer to 50 nm or less, a method using a base film in which the surface roughness SRa of the surface on which the release layer is laminated is 60 nm or less is preferable. Furthermore, the release layer preferably contains no particles or, if it contains particles, a small amount. The content of particles in the case where the release layer contains particles is preferably 3.0% by mass or less and 1.0% by mass or less based on 100% by mass of the total solid content of the release layer. Is more preferably 0.5% by mass or less.

  Here, the surface roughness SRa can be measured using an optical interference microscope, for example, “VertScan” manufactured by Ryoka Systems Co., Ltd.

[Base film]
It does not specifically limit as a base film used for the release film of this invention, Various plastic films can be used. For example, polyester film such as polyethylene terephthalate film, polybutylene terephthalate film, polyethylene naphthalate film, polyolefin film such as polypropylene film, polyethylene film, cellulose film such as diacetyl cellulose film, triacetyl cellulose film, polysulfone film, polyether ether ketone Films, polyethersulfone films, polyphenylene sulfide films, polyetherimide films, polyimide films, polyamide films, acrylic films, cyclic olefin films, polycarbonate films and the like can be mentioned.

  Among these plastic films, polyimide film polyester film and cyclic olefin film having good heat resistance are preferable, and polyester film is particularly preferable. As a polyester film, a polyethylene terephthalate film is preferable, and a biaxially stretched polyethylene terephthalate film is more preferable.

  When using a polyester film as a base film, the polyester film of 3 layer laminated constitution is preferable from a viewpoint of controlling surface roughness SRa of a base film. As a three-layer lamination configuration, A layer / B layer / A layer or A layer / B layer / C layer can be mentioned. Here, the layer A, the layer B and the layer C mean that their compositions are different.

  In the above three-layer configuration, the layer A or layer C preferably contains particles. The surface roughness SRa of the polyester film can be controlled by adjusting the average particle size and / or the content of the particles contained in the layer A or the layer C.

  60 nm or less is preferable, 50 nm or less is more preferable, and, as for surface roughness SRa of the side which laminates | stacks the mold release layer of a base film, 30 nm or less is especially preferable. The surface roughness SRa is preferably 1 nm or more, more preferably 3 nm or more, and particularly preferably 5 nm or more, from the viewpoint of securing the slip property and winding of the release film.

  From the viewpoint of simplification of production facilities and improvement of productivity, a polyester film having a three-layer lamination structure of A layer / B layer / A layer is preferably used.

  10-200 micrometers is preferable, as for the thickness of a base film, 15-150 micrometers is more preferable, and 20-100 micrometers is especially preferable.

[Anchor Layer]
It is preferable to arrange an anchor layer for improving the adhesion between the base film and the release layer, between the base film and the release layer.

  The anchor layer contains a silane compound and a metal complex having an organic ligand from the viewpoint of improving the adhesion between the substrate film (particularly polyester film) and the release layer containing the silicone-modified alkyd resin. Is preferred.

  As the silane compound, a compound represented by the following general formula (1), or a condensate or partial condensate of a hydrolyzate of the compound is preferably used.

Si (X) a (Y) b (R) c ・ ・ ・ General formula (1)
(Wherein X represents a group in which one member selected from the group consisting of glycidoxy group, mercapto group, (meth) acryloxy group and amino group is bonded to an alkylene group, an alkenyl group, a vinyl group or a haloalkyl group; A hydrolysable group is represented, R is a hydrocarbon group, a is 0 or 1, b is 2 or 3, c is an integer of 0 to 2, and a + b + c = 4.
Examples of the hydrolyzable group represented by Y include a methoxy group, an ethoxy group, a butoxy group, an isopropenoxy group, an acetoxy group, a butanoxym group, a ketoxime group, an amino group and the like, and one or more of these may be used in combination. Can. Among them, methoxy and ethoxy are preferable because they have good hydrolyzability.

  The hydrocarbon group represented by R is preferably a hydrocarbon group having 1 to 12 carbon atoms, and specifically, methyl group, ethyl group, propyl group, hexyl group, octyl group, decyl group, phenyl group, A cyclohexyl group etc. are mentioned.

  As the silane compound represented by the general formula (1), specifically, methyltrimethoxysilane, methyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane Hexyltrimethoxysilane, hexyltriethoxysilane, cyclohexyltrimethoxysilane, octyltriethoxysilane, decyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane, allyltrimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane , 3-mercaptopropyltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyl ester -Diethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-acryloxypropylmethyldiethoxysilane, 3-acryloxypropyltriethoxysilane, 3-aminopropyltriethoxysilane, N 2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) Propylamine, N-phenyl-3-aminopropyltrimethoxysilane, 5-hexenyltrimethoxysilane, trifluoropropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, -Glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropylmethyldiisopropenoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, vinyl tri Methoxysilane, vinyltriethoxysilane, vinylmethyldimethoxysilane and the like can be mentioned.

  The central metal of the metal complex having an organic ligand is preferably at least one selected from the group consisting of aluminum, zirconium and titanium. Among them, aluminum and zirconium are preferable, and aluminum is particularly preferable. Further, the metal complex having an organic ligand is preferably a chelate compound having the central metal, particularly preferably an aluminum chelate compound.

  Specific examples of metal complexes having an organic ligand and having aluminum as a central metal include bis (ethylacetoacetate) (2,4-pentanedionate) aluminum, aluminum tris (acetylacetonate), aluminum tris (Ethylacetoacetate), aluminum monoacetylacetonate bis (ethylacetoacetate), aluminum-di-n-butoxide-monoethylacetoacetate, aluminum-di-isopropoxide-monomethylacetoacetate and the like.

  Specific examples of metal complexes having an organic ligand and having zirconium as a central metal include, for example, zirconium acetate, zirconium normal propylate, zirconium normal butyrate, zirconium tetraacetylacetonate, zirconium monoacetylacetonate, and zirconium bis. And acetylacetonate.

  Specific examples of the metal complex having an organic ligand and having titanium as a central metal include, for example, titanium such as tetranormal butyl titanate, tetraisopropyl titanate, butyl titanate dimer, tetra (2-ethylhexyl) titanate, tetramethyl titanate and the like. Orthoesters, titanium acetylacetonate, titanium tetraacetylacetonate, polytitanium acetylacetonate, titanium octylene glycolate, titanium lactate, titanium triethanolaminate, titanium ethylacetoacetate, titanium diisopropoxy bis (ethylacetoacetate) Etc.).

  10-200 nm is preferable, as for the thickness of an anchor layer, 20-150 nm is more preferable, and 30-100 nm is especially preferable.

[Transfer layer]
The transfer layer in the present invention contains at least one selected from the group consisting of an epoxy compound and a compound having an ethylenically unsaturated group in the molecule. The transfer layer is formed by applying a composition containing at least one selected from the group consisting of an epoxy compound and a compound having an ethylenically unsaturated group in the molecule onto the release layer of the release film, and optionally drying it, It is cured and formed.

  The composition containing an epoxy compound is preferably a thermosetting composition or an active energy ray curable composition.

  The composition containing a compound having an ethylenically unsaturated group in the molecule is preferably an active energy ray curable composition.

  The thermosetting composition is a composition which is cured by heating, and the heating temperature is generally 100 to 200 ° C., and preferably 120 to 180 ° C.

  An active energy ray-curable composition is a composition that cures upon irradiation with active energy rays. As an active energy ray, an ultraviolet ray, a visible ray, infrared rays, an electron beam, an alpha ray, a beta ray, a gamma ray etc. are mentioned. Among them, ultraviolet rays and electron beams are preferable, and ultraviolet rays are particularly preferably used.

  The curing time of the transfer layer when the transfer layer is composed of a thermosetting composition or an active energy ray curable composition is not particularly limited, and the kind of the compound contained in the transfer layer, the type and use of the transfer layer, and the object It is appropriately selected depending on the type and use of the garment.

  Specifically, the curing time of the transfer layer can be implemented by any of a step of laminating the transfer layer on the release layer of the release film, a transfer step of the transfer layer, and after transfer. Also, it can be divided and cured in two or more steps. Details of the curing time of the transfer layer will be described later.

  The content of at least one compound selected from the group consisting of an epoxy compound in the transfer layer and a compound having an ethylenically unsaturated group in the molecule is preferably 5% by mass or more based on 100% by mass of the total solid content of the transfer layer. 10 mass% or more is more preferable, and 20 mass% or more is especially preferable. The upper limit is 100% by mass. The above content means the total content when the transfer layer contains two or more compounds.

  As the transfer layer in the present invention, that is, the transfer layer containing at least one selected from the group consisting of compounds having an ethylenically unsaturated group in the molecule, various functional layers can be mentioned. For example, an adhesive layer, a sealing resin layer of a circuit board, an interlayer insulating resin layer of a multilayer printed wiring board, a hard coat layer, an antifouling layer, an antireflective layer, a photosensitive resin layer, a self-healing resin layer Resin layer), an antistatic layer, a near infrared ray absorbing layer, an ultraviolet ray absorbing layer, a conductive layer, an antifogging layer, a protective layer of an automobile exterior coating (anti-chipping layer) and the like.

  As a preferable example of the transfer layer containing an epoxy compound, an adhesive bond layer, the sealing resin layer of a circuit board, and the interlayer insulation resin layer of a multilayer printed wiring board are mentioned. The sealing resin layer and the interlayer insulating resin layer are often adhesive layers, and in this case, the sealing resin layer and the interlayer insulating resin layer are included in the adhesive layer. That is, the adhesive layer in the present invention is preferably a sealing resin layer of a circuit board and an interlayer insulating resin layer of a multilayer printed wiring board.

  Preferred examples of the transfer layer containing a compound having an ethylenically unsaturated group in the molecule include a hard coat layer, an antifouling layer, and an antireflective layer.

  That is, the transfer layer in the present invention is preferably at least one layer selected from the group consisting of an adhesive layer, a hard coat layer, an antifouling layer and an antireflective layer. Details will be described later.

[Epoxy compound]
The epoxy compound is not particularly limited, and known compounds can be used. For example, an epoxy compound (epoxy resin) used for a sealing resin of a circuit board or an interlayer insulating resin of a multilayer printed wiring board, an epoxy compound (epoxy resin) used for a thermosetting adhesive, or the like can be used.

  Specific examples of the epoxy compound (epoxy resin) include bisphenol A epoxy resin, bisphenol F epoxy resin, phenol novolac epoxy resin, cresol novolac epoxy resin, bisphenol S epoxy resin, alkylphenol novolac epoxy resin, biphenol epoxy resin Naphthalene type epoxy resin, dicyclopentadiene type epoxy resin, epoxy compound of condensate of phenol and aromatic aldehyde having phenolic hydroxyl group, triglycidyl isocyanurate, aliphatic cyclic epoxy resin, glycidyl ester type epoxy resin, glycidyl amine Type epoxy resin, hydantoin type epoxy resin, isocyanurate type epoxy resin, acrylic acid modified epoxy resin (epoxy acrylate), naphthale Type epoxy resins, linear aliphatic epoxy resins, heterocyclic epoxy resins, spiro ring-containing epoxy resins, and halogenated epoxy resins.

  As such an epoxy resin, specifically, HP4032, HP4032D, HP4700, N-690, N-695 manufactured by Dainippon Ink & Chemicals, Inc., "Epicoat (registered trademark) manufactured by Japan Epoxy Resins Co., Ltd." And the like, and "EPPN (registered trademark)" of Nippon Kayaku Co., Ltd.-502 H, NC 7000 L, NC 3000 H, ESN 185, ES N 475, etc. manufactured by Toto Kasei Co., Ltd.

[Compound having an ethylenically unsaturated group in the molecule]
Examples of the ethylenically unsaturated group of the compound having an ethylenically unsaturated group in the molecule include a vinyl group, an allyl group, an acryloyl group, a methacryloyl group, an acryloyloxy group and a methacryloyloxy group. Among these, acryloyloxy group and methacryloyloxy group are preferable. As such compounds, (meth) acrylate compounds are generally known.

  Hereinafter, although the compound which has an ethylenically unsaturated group in a molecule | numerator is illustrated, it is not limited to these compounds. In the following description, "... (meth) acrylate" is a generic term for "... acrylate" and "... methacrylate".

Examples of compounds having an ethylenically unsaturated group in the molecule include methyl (meth) acrylate, lauryl (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, methoxytriethylene glycol (meth) acrylate and phenoxyethyl (meth) acrylate Monofunctional compounds such as tetrahydrofurfuryl (meth) acrylate, isobornyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxy-3-phenoxy (meth) acrylate Meta) acrylate,
Ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, diethylene glycol Di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, etc. Bifunctional (meth) acrylate,
Trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, glycerin propoxy tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate , Dipentaerythritol tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol tri (meth) acrylate, tripentaerythritol hexa Examples thereof include 3 to 6 functional (meth) acrylates such as (meth) acrylates.

  Moreover, as a compound which has an ethylenically unsaturated group in a molecule | numerator, the compound which has an ethylenically unsaturated group and a urethane bond in a molecule | numerator is mentioned. For example, ethylene glycol, adipic acid, tolylene diisocyanate, 2-hydroxyethyl (meth) acrylate, polyethylene glycol, tolylene diisocyanate, 2-hydroxyethyl (meth) acrylate, hydroxyethyl phthalyl (meth) acrylate, xylene diisocyanate, 1 , 2-polybutadiene glycol tolylene diisocyanate · 2-hydroxyethyl (meth) acrylate, trimethylolpropane · propylene glycol · tolylene diisocyanate · 2-hydroxyethyl (meth) acrylate, pentaerythritol tri (meth) acrylate hexamethylene diisocyanate urethane Pre-oligomer, pentaerythritol tri (meth) acrylate toluene diisocyanate urethane Mer, pentaerythritol tri (meth) acrylate isophorone diisocyanate urethane oligomer and the like.

  Moreover, as a compound which has an ethylenically unsaturated group and a urethane bond in a molecule | numerator, urethane (meth) acrylate of polyether frame | skeleton, urethane (meth) acrylate of polycaprolactone frame | skeleton, and urethane (meth) acrylate of polycarbonate frame | skeleton are mentioned.

  Examples of the urethane (meth) acrylate having a polyether skeleton include the following compound (1a) and compound (1b).

(1a); compound obtained by reacting polyalkylene glycol (meth) acrylate and isocyanate compound (1b); reaction of polyalkylene glycol and isocyanate compound in such a ratio that the isocyanate group is excessive to the hydroxyl group The compound obtained by reacting the (meth) acrylate compound which further has a hydroxyl group with the compound obtained by making it be obtained. The polyalkylene glycol (meth) acrylate compound used for the synthesis of the above (1a) is, for example, polyethylene glycol Examples include meta) acrylates, polypropylene glycol (meth) acrylates, polybutylene glycol (meth) acrylates, and the like.

  The isocyanate compound used in the synthesis of the above (1a) is preferably a polyisocyanate compound having two or more isocyanate groups in the molecule, and, for example, tolylene diisocyanate, naphthalene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, xylylene diisocyanate, Tetramethylene diisocyanate, hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, methyl-2,6-diisocyanatohexanoate, norbornane diisocyanate, methylenebis-4-cyclohexylisocyanate, tolylene diisocyanate Methylol propane adduct, hexamethylene diisocyanate Methylol propane adduct, trimethylol propane adduct of isophorone diisocyanate, isocyanurate of tolylene diisocyanate, isocyanurate of hexamethylene diisocyanate, (poly) isocyanate such as biuret of hexamethylene isocyanate, and block of the above isocyanate And the like.

  As a polyalkylene glycol used for the synthesis | combination of said (1b), polyethyleneglycol, a polypropylene glycol, a polybutylene glycol etc. are mentioned, for example.

  As an isocyanate compound used for the synthesis | combination of said (1b), the compound similar to the isocyanate compound used for the synthesis | combination of said (1a) can be used.

  Examples of the (meth) acrylate compound having a hydroxyl group used in the synthesis of the above (1b) include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2 -Hydroxy-3-phenoxypropyl (meth) acrylate, 2- (meth) acryloyloxyethyl-2-hydroxyethyl-phthalic acid, 2-hydroxy-3-acryloyloxypropyl (meth) acrylate, polyethylene glycol mono (meth) acrylate ) Acrylates, polypropylene glycol mono (meth) acrylates, glycerol mono (meth) acrylates, pentaerythritol tri (meth) acrylates, dipentaerythritol penta (meth) acrylates, polycaprolactone-modified aa Etc. Kill (meth) acrylate.

  Examples of the polycaprolactone skeleton urethane (meth) acrylate compound include the following compound (2a), compound (2b) and compound (2c).

(2a); compound obtained by reacting polycaprolactone modified alkyl (meth) acrylate with isocyanate compound (2b); compound obtained by reacting polycaprolactone modified hydroxyalkyl (meth) acrylate with isocyanate compound (2c) Compound obtained by reacting long-chain alkyl alcohol, polycaprolactone modified hydroxyethyl (meth) acrylate and isocyanate compound Here, as an isocyanate compound, the same compound as the isocyanate compound used for the synthesis of the above (1a) Can be used.

  The urethane (meth) acrylate compound having a polycarbonate skeleton can be synthesized by reacting a polycarbonate polyol, an isocyanate compound and a (meth) acrylate having a hydroxyl group.

  The polycarbonate polyol can be produced by transesterification reaction of alkylene glycol and carbonate, or reaction of phosgene or chloroformate with alkylene glycol, or the like.

  As an alkylene glycol, for example, ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,9-nonanediol, 1,10-decanediol, neopentyl Glycol, 3-methyl-1,5-pentanediol, 2,4-diethyl-1,5 pentanediol, 2-methyl-1,8-octanediol, 1,4-cyclohexanediol, bisphenol A, glycerin, trimethylol Propane, pentaerythritol and the like can be mentioned.

  Examples of carbonates include methyl carbonate, dimethyl carbonate, ethyl carbonate, diethyl carbonate, n-propyl carbonate, di-n-propyl carbonate, isopropyl carbonate, diisopropyl carbonate, n-butyl carbonate, di-n-butyl carbonate, isobutyl Carbonate, diisobutyl carbonate, cyclocarbonate, diphenyl carbonate, methyl diphenyl carbonate, ethylene carbonate, 1,2-propylene carbonate, 1,2-butylene carbonate and the like can be mentioned.

  Moreover, as a compound which has an ethylenically unsaturated group in a molecule | numerator, the compound which has an ethylenically unsaturated group and a fluorine atom in a molecule | numerator is mentioned. Such compounds include, for example, trifluoroethyl (meth) acrylate, tetrafluoropropyl (meth) acrylate, pentafluoropropyl (meth) acrylate, hexafluoropropyl (meth) acrylate, octafluoropentyl (meth) acrylate, perfluorobutyl Ethyl (meth) acrylate, perfluorobutylhydroxypropyl (meth) acrylate, perfluorohexylethyl (meth) acrylate, perfluorohexylhydroxypropyl (meth) acrylate, perfluorooctylethyl (meth) acrylate, perfluorooctylhydroxypropyl ( Meta) acrylate, perfluorodecylethyl (meth) acrylate, heptadecafluorodecyl (meth) acrylate, divinyl Decafluorohexane, divinylhexadecafluorooctane, 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3,3-pentafluoropropyl (meth) acrylate, 2- (perfluorobutyl) ethyl (Meth) acrylate, 2- (perfluorohexyl) ethyl (meth) acrylate, 2- (perfluorooctyl) ethyl (meth) acrylate, 2- (perfluorodecyl) ethyl (meth) acrylate, β- (perfluoro octyl) ) Ethyl (meth) acrylate, di- (α-fluoroacrylic acid) -2,2,2-trifluoroethyl ethylene glycol, di- (α-fluoroacrylic acid) -2,2,3,3,3-penta Fluoropropyl ethylene glycol, di- (α-fluoroacrylic acid) -2,2,3, 3,4,4,4-hexafluorobutyl ethylene glycol, di- (α-fluoroacrylic acid) -2,2,3,3,4,4,5,5,5-nonafluoropentyl ethylene glycol, di- (Α-fluoroacrylic acid) -2,2,3,3,4,4,5,5,6,6,6-undecafluorohexyl ethylene glycol, di- (α-fluoroacrylic acid) -2,2 3,3,4,4,5,5,6,6,7,7,7-tridecafluoroheptyl ethylene glycol, di- (α-fluoroacrylic acid) -2,2,3,3,4,6 4,5,5,6,6,7,7,8,8,8-Pentadecafluorooctyl ethylene glycol, di- (α-fluoroacrylic acid) -3,3,4,4,5,5,6 6,7,7,8,8,8-tridecafluorooctyl ethylene glycol Cole, di- (α-fluoroacrylic acid) -2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,9,9-heptadecafluorononyl Ethylene glycol etc. are mentioned.

  Moreover, as a compound which has an ethylenically unsaturated group in a molecule | numerator, the polysiloxane compound which has an ethylenically unsaturated group is mentioned. As such a compound, a compound having an ethylenically unsaturated group at both ends and / or side chains of the polysiloxane main chain is preferable.

  As the polysiloxane compound having an ethylenically unsaturated group, compounds of Production Examples 1-1 to 1-3 of JP 2009-84327 A, or Silaprene FM-0711 and FM 07021 manufactured by Chisso Corporation. FM-0725, Shin-Etsu Chemical Co., Ltd. X-24-8201, X-22-174DX, X-22-1602, X22-1603, X-22-2426, X-22-2404, X- 22-164A, X-22-164C, X-22-2458, X-22-2459, X-22-2445, X-22-2457, BY16-152D manufactured by Toray Dow Corning Co., Ltd., BY16-152 Commercial products such as BY16-152C and BYK-UV 3570 manufactured by Big Chemie Japan Co., Ltd. can be used.

[Adhesive layer]
The transfer layer in the present invention is preferably an adhesive layer. The adhesive layer preferably contains an epoxy compound. The adhesive layer is a thermosetting composition containing an epoxy compound, an active energy ray curable composition, or a cured product of a thermally active energy ray curable composition containing a thermosetting component and an active energy ray curable component. Is preferred. As the epoxy compound, the above-mentioned epoxy resin is preferably used. Among them, an adhesive layer (thermosetting adhesive layer) composed of a cured product of a thermosetting composition containing an epoxy compound is preferable.

  The adhesive layer is suitable, for example, as a sealing resin layer of a circuit board or an interlayer insulating resin layer of a multilayer printed wiring board. In particular, as the adhesive layer applied to the above-mentioned applications, it is preferable to be an adhesive layer (thermosetting adhesive layer) formed of a cured product of a thermosetting composition containing an epoxy compound.

  Hereinafter, a thermosetting adhesive layer suitable for a sealing resin layer of a circuit board or an interlayer insulating resin layer of a multilayer printed wiring board will be described in detail.

  The adhesive layer can contain the above-described epoxy compound and another thermosetting resin other than the epoxy compound. As another thermosetting resin, the novolak-type phenol resin bridge | crosslinked with an epoxy resin, vinyl phenol resin, brominated vinyl phenol etc. are mentioned, for example.

  The adhesive layer preferably further contains a curing agent. Examples of curing agents include amine curing agents, guanidine curing agents, imidazole curing agents, phenol curing agents, acid anhydride curing agents, hydrazide curing agents, carboxylic acid curing agents, thiol curing agents or These epoxy adducts and microcapsules may be mentioned. Moreover, you may use together and use hardening accelerators, such as a triphenyl phosphine, a phosphonium borate, 3- (3, 4- dichlorophenyl) -1,1- dimethyl urea.

  Specific examples of the curing agent include, for example, dicyandiamide, 4,4'-diaminodiphenyl sulfide, 3,3'-diaminobenzophenone, 3,3'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfone, 3,4 '-Diaminodiphenyl sulfone, 3,4,4'-triaminodiphenyl sulfone, 3,3', 5,5'-tetramethyl-4,4'-diaminodiphenylmethane, 3,3'-dichloro-4,4 ' -Diaminodiphenylmethane, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2,4-diamino-6- (2-methyl-1-imidazolylethyl) -1,3,5-triazine isocyanuric acid adduct, Examples thereof include triazine structure-containing novolak resins, phenol resins, and melamine resins.

  The adhesive layer can contain a thermoplastic resin. As a thermoplastic resin, acrylonitrile-butadiene copolymer (NBR), carboxylated acrylonitrile-butadiene copolymer (carboxylated NBR), acrylonitrile-butadiene-styrene copolymer (ABS), polybutadiene, styrene-butadiene-ethylene copolymer Polymer (SEBS), (meth) acrylic ester resin (acrylic rubber), carboxylated ethylene acrylic rubber, polyvinyl butyral, polyamide, polyester, polyimide, polyamide imide, polyurethane and the like can be mentioned.

  The adhesive layer can contain an inorganic or organic filler. As the inorganic filler, for example, silica, alumina, barium sulfate, talc, clay, mica powder, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, magnesium oxide, boron nitride, aluminum borate, barium titanate, Strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, barium zirconate, calcium zirconate and the like can be mentioned. Examples of the organic filler include acrylic rubber particles and silicone particles.

  The adhesive layer is preferably heat-cured after the transfer step or transfer. Here, heating in the transfer step means heating in the presence of the release film, and heating after transfer means heating after the release film is peeled off. As heating temperature, 100-200 degreeC is common, and 120-180 degreeC is preferable.

  When the adhesive layer is an adhesive layer comprising a cured product of an active energy ray curable composition, it contains the above-mentioned epoxy compound, a compound having an ethylenically unsaturated group in the molecule, and a photopolymerization initiator. Is preferred. Furthermore, the above-mentioned thermoplastic resin and inorganic or organic filler can be contained. The adhesive layer is preferably cured by irradiation with active energy rays after the transfer step or transfer.

  When the adhesive layer is an adhesive layer comprising a cured product of a heat / active energy ray curable composition, the above-mentioned epoxy compound, the above-mentioned curing agent, a compound having an ethylenically unsaturated group in the molecule, light It is preferable to contain a polymerization initiator. Furthermore, the above-mentioned thermoplastic resin and inorganic or organic filler can be contained. The adhesive layer is preferably cured by heating and / or irradiation with active energy rays after the transfer step or transfer.

  Here, as the compound having an ethylenically unsaturated group in the molecule, the same compounds as described above can be used. Moreover, the compound similar to the compound used for a below-mentioned hard-coat layer can be used for a photoinitiator.

  10-200 micrometers is suitable for the thickness of an adhesive bond layer, and 20-100 micrometers is preferable.

[Hard coat layer]
The transfer layer in the present invention is preferably a hard coat layer. The hard coat layer is applied to inhibit scratching of the adherend such as the plastic resin molded product described above or to provide a design.

  The pencil hardness (defined in JIS K 5600-5-4 (1999)) of the hard coat layer is preferably F or more from the viewpoint of exerting the scratching suppression effect on the adherend to which the hard coat layer has been transferred. The above is more preferable, and 2H or more is particularly preferable. The upper limit is about 9H.

  The hard coat layer preferably contains a compound having an ethylenically unsaturated group in the molecule. That is, the hard coat layer is preferably made of a cured product of an active energy ray curable composition containing a compound having an ethylenically unsaturated group in the molecule.

  From the viewpoint of increasing the pencil hardness of the hard coat layer and suppressing the cure shrinkage, the active energy ray curable composition for forming the hard coat layer is a compound having an ethylenically unsaturated group and a urethane bond in the molecule. It is preferable to contain The composition is more preferably used in combination with the aforementioned 3- to 6-functional (meth) acrylate in addition to the compound having an ethylenically unsaturated group and a urethane bond in the molecule.

  The active energy ray-curable composition preferably further contains a photopolymerization initiator.

  Specific examples of such photopolymerization initiators include, for example, acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone, benzophenone, 2-chlorobenzophenone, 4,4'-dichlorobenzophenone, 4,4'-Bisdiethylaminobenzophenone, Michler's ketone, benzyl, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, methyl benzoyl formate, p-isopropyl-α-hydroxyisobutylphenone, α-hydroxyisobutylphenone, 2, Carbonyl compounds such as 2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexyl phenyl ketone, tetramethylthiuram monosulfide, teto It is possible to use sulfur compounds such as lamethylthiuram disulfide, thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone and the like. These photopolymerization initiators may be used alone or in combination of two or more.

  Also, photoinitiators are generally commercially available, and they can be used. For example, “Irgacure (registered trademark)” 184, Irgacure 907, Irgacure 379, Irgacure 819, Irgacure 127, Irgacure 500, Irgacure 754, Irgacure 250, Irgacure 1800, Irgacure 1870, Irgacure 1870, Irgacure OXE01 manufactured by Ciba Specialty Chemicals Inc. , DAROCUR TPO, DAROCUR 1173, etc., Speedcure MBB, Speedcure PBZ, Speedcure ITX, Speedcure CTX, Speedcure EDB, Esacure ONE, Esacure KIP 150, Esacure KTO 46, etc. manufactured by Nippon Sibel Hegner Ltd., KAYACURE DETX-S, KAYACURE C, manufactured by Nippon Kayaku Co., Ltd. KAYAC RE BMS, KAYACURE DMBI, and the like.

  In the case of imparting antifouling properties (fingerprint resistance) to the hard coat layer, it contains a compound having an ethylenically unsaturated group and a fluorine atom in the molecule and / or a polysiloxane compound having an ethylenically unsaturated group in the molecule. It is preferable to

  The hard coat layer may further contain particles, pigments, UV absorbers, antistatic agents and the like.

  0.5-20 micrometers is suitable for the thickness of a hard-coat layer, 1-15 micrometers is preferable, and 2-10 micrometers is more preferable.

  The hard coat layer can be formed by applying an active energy ray-curable composition on the release layer of the release film, drying if necessary, and then irradiating the active energy ray. The active energy includes ultraviolet light, visible light, infrared light, electron beam, α rays, β rays, γ rays and the like. Among them, ultraviolet rays and electron beams are preferable, and ultraviolet rays are particularly preferably used.

  Although it does not specifically limit as a light source for irradiating an ultraviolet-ray, For example, an ultraviolet fluorescent lamp, a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a carbon arc lamp, a metal halide lamp, a xenon lamp etc. can be used. . In addition, an ArF excimer laser, a KrF excimer laser, an excimer lamp, synchrotron radiation or the like can be used. Among these, an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc, a xenon arc and a metal halide lamp are preferably used. When ultraviolet light is irradiated, it is preferable to perform irradiation under an atmosphere of low oxygen concentration, for example, under an atmosphere of oxygen concentration of 500 ppm or less, because curing can be performed efficiently.

Irradiation light amount of the ultraviolet rays is preferably from 50 mJ / cm ² or more, 100 mJ / cm ² or more, and particularly 150 mJ / cm ² or more. The upper limit is preferably 2000 mJ / cm ² or less, more preferably 1000 mJ / cm ² or less.

  As a coating method of the active energy ray curable composition, for example, coating methods such as reverse coating method, spray coating method, bar coating method, gravure coating method, rod coating method, die coating method, spin coating method, extrusion coating method and the like Can be used.

  The curing time of the hard coat layer may be almost completely cured in the step of laminating the hard coat layer on the release layer of the release film, or may be divided and divided into two steps. The divisional curing may be, for example, a method of semi-curing in the step of laminating the hard coat layer, and in the step of transferring the hard coat layer or after the transfer, the active energy ray is irradiated for complete curing.

[Antifouling layer]
The transfer layer in the present invention is preferably an antifouling layer. The antifouling layer is a layer having a function of suppressing adhesion of a soiling component such as a fingerprint or a function of wiping off even when a soiling component such as a fingerprint adheres. Such a function can be represented, for example, by the water contact angle of the surface of the antifouling layer. That is, the water contact angle on the surface of the antifouling layer is preferably 90 degrees or more, more preferably 95 degrees or more, and particularly preferably 100 degrees or more. The upper limit is about 160 degrees.

  The antifouling layer is applied to impart antifouling properties to a plastic resin molded product which is an adherend.

  The antifouling layer preferably contains a compound having an ethylenically unsaturated group and a fluorine atom in the molecule and / or a polysiloxane compound having an ethylenically unsaturated group in the molecule.

  The antifouling layer comprises a cured product of an active energy ray curable composition containing a compound having an ethylenically unsaturated group and a fluorine atom in the molecule and / or a polysiloxane compound having an ethylenically unsaturated group in the molecule. Is preferred. That is, the antifouling layer can be formed by applying the above-mentioned active energy ray-curable composition on the release layer of the release film, drying it as necessary, and then irradiating the active energy ray to cure it. . The irradiation conditions of the active energy ray may be the same as the conditions in the above-mentioned hard coat layer.

  The active energy ray-curable composition preferably further contains the above-mentioned 2 to 6 functional (meth) acrylate. The active energy ray curable composition preferably further contains a photopolymerization initiator. As the photopolymerization initiator, the same compounds as those used for the hard coat layer can be used.

  0.01-10 micrometers is preferable, as for the thickness of an antifouling layer, 0.02-5 micrometers is more preferable, and 0.03-3 micrometers is especially preferable.

[Anti-reflection layer]
The transfer layer in the present invention is preferably an antireflective layer. The antireflective layer is applied to provide an antireflective property to a plastic resin molded product as an adherend. From this viewpoint, the antireflection layer preferably has a refractive index of 1.47 or less at a wavelength of 589 nm, more preferably 1.43 or less, and still more preferably 1.40 or less. The lower limit is about 1.25.

  The antireflective layer preferably contains a compound having an ethylenically unsaturated group in the molecule, a fluorine compound and / or hollow silica.

  The antireflective layer preferably comprises a cured product of an active energy ray-curable composition containing a compound having an ethylenically unsaturated group in the molecule, and a fluorine compound and / or hollow silica. That is, the antireflective layer can be formed by applying the above-mentioned active energy ray curable composition on the release layer of the release film, drying it as necessary, and then irradiating and curing the active energy ray. . The irradiation conditions of the active energy ray may be the same as the conditions in the above-mentioned hard coat layer.

  As a fluorine compound, the compound which has an ethylenically unsaturated group and a fluorine atom in the above-mentioned molecule | numerator is used preferably. In this case, the “compound having an ethylenically unsaturated group in the molecule” other than the fluorine compound is not necessarily required, but from the viewpoint of increasing the hardness of the antireflective layer, the above-mentioned 2 to 6 functional (meth) It is preferable to contain an acrylate.

  The active energy ray curable composition preferably further contains a photopolymerization initiator. As the photopolymerization initiator, the same compounds as those used for the hard coat layer can be used.

  As a particularly preferable embodiment of the antireflective layer, an embodiment containing hollow silica and a 2 to 6 functional (meth) acrylate as a compound having an ethylenically unsaturated group in the molecule can be mentioned.

  The thickness of the antireflective layer is preferably 0.08 to 0.12 μm, and more preferably 0.09 to 0.11 μm.

[Transfer film]
The transfer film of the present invention is obtained by laminating a transfer layer containing at least one selected from the group consisting of an epoxy compound and a compound having an ethylenically unsaturated group in the molecule on the release layer of the release film. is there.

  In the following description, the “transfer layer containing at least one selected from the group consisting of an epoxy compound and a compound having an ethylenically unsaturated group in the molecule” may be referred to as “first transfer layer”.

  In the transfer film of the present invention, the second transfer layer may be laminated on the side opposite to the release film of the first transfer layer. That is, the transfer film of the present invention includes a mode in which the first transfer layer is directly laminated on the release layer of the release film, and the second transfer layer is laminated on the first transfer layer. Here, the second transfer layer may be composed of a single layer or multiple layers.

  The second transfer layer is appropriately selected depending on the type and use of the first transfer layer, or the type and use of the adherend. When the first transfer layer is a hard coat layer, an antifouling layer or an antireflective layer, the second transfer layer includes an adhesive layer for bringing the first transfer layer into close contact with the adherend, and an adhesion to the first transfer layer An adhesion strengthening layer for improving the adhesion of a layer etc. are mentioned.

  As the adhesive layer, for example, a resin adhesive or a hot melt adhesive can be used. As the adhesive, for example, acrylic acid ester type, polyester type, synthetic rubber type, epoxy type, polyurethane type, ethylene-vinyl acetate type, polyamide type, polyvinyl chloride, halogenated polyolefin, nitrocellulose, and copolymers thereof Etc. As a hot melt type adhesive agent, the thing of polyurethane, a polyamide, a polyvinyl chloride type is mentioned, for example.

  As a material which comprises an adhesion reinforcement layer, thermosetting resin, such as an acryl urethane resin, a salt vinyl-acetate resin, a polyester-type resin, a melamine-type resin, and an epoxy type, is mentioned preferably.

  As a 2nd transfer layer in case a 1st transfer layer is an antifouling layer, a hard court layer is mentioned further. The hard coat layer is preferably disposed between the antifouling layer and the above-mentioned adhesive layer or adhesion enhancing layer. As the hard coat layer, the same configuration as that of the hard coat layer constituting the first transfer layer described above can be adopted.

  As a 2nd transfer layer in case a 1st transfer layer is an anti-reflective layer, a hard-coat layer, a high refractive index layer, a high refractive index hard-coat layer etc. are mentioned further. These layers are preferably disposed between the antireflective layer and the aforementioned adhesive layer or adhesion enhancing layer.

  As the hard coat layer, the same configuration as that of the hard coat layer constituting the first transfer layer described above can be adopted.

  The high refractive index layer and the high refractive index hard coat layer preferably have a refractive index of 1.55 to 1.80 at a wavelength of 589 nm. The high refractive index layer and the high refractive index hard coat layer are cured products of an active energy ray curable composition containing high refractive index metal oxide fine particles and a compound having an ethylenically unsaturated group in the aforementioned molecule. Is preferred. Examples of metal oxide fine particles having a high refractive index include zirconium oxide, titanium oxide, zinc oxide, tin oxide, antimony oxide, tin oxide-doped indium oxide (ITO), and antimony-doped tin oxide (ATO).

  0.08-0.20 micrometer is preferable and, as for the thickness of a high refractive index layer, 0.09-0.17 micrometer is more preferable. 0.5-5.0 micrometers is preferable and, as for the thickness of a high refractive index hard-coat layer, 0.7-3.0 micrometers is more preferable.

  Hereinafter, the present invention will be described in detail by way of examples, but the present invention is not limited to these examples.

[Measuring method and evaluation method]
(1) Measurement of surface free energy of mold release layer Water, diiodomethane, 1-bromonaphthalene as three kinds of liquids whose values of surface free energy and each component (dispersion power, polarity power, hydrogen bonding power) are known The contact angle of each liquid on the release layer was measured using a contact angle meter DropMaster DM 501 (manufactured by Kyowa Interface Science Co., Ltd.) at 23 ° C. and 65% RH. The measurement was performed 5 times for one measurement surface, and the average value was taken as the contact angle (θ). From the values of the contact angle (θ) and the known values of each liquid (method IV of Panzer (described in Japan Adhesive Association Vol. 15, No. 3, page 96), introduced from Kitazaki-Hata equation The value of each component was calculated using the following equation.

(ΓSd · γLd) 1/2 + (γSp · γLp) 1/2 + (γSh · γLh) 1/2 = γL (1 + cos θ) / 2
Here, γLd, γLp, and γLh respectively represent the dispersion force, polarity force, and hydrogen bonding force components of the measurement solution, θ represents the contact angle of the measurement solution on the measurement surface, and γSd, γSp, γSh represents values of the dispersion force, polarity force, and hydrogen bonding force components of the laminated film surface, respectively, and γL represents the surface energy of each liquid. The values of three components of the measurement surface (release layer surface) are determined by solving the simultaneous equations obtained by substituting known values and θ into the above equation.

  The sum of the value of the dispersion force component, the value of the polar force component, and the value of the hydrogen bonding component is determined as the value of the surface free energy (E) as in the following formula.

E = γSd + γSp + γSh
(2) Measurement of Surface Roughness SRa The surface roughness SRa of the substrate film and the release layer is an optical interference type microscope (manufactured by Ryoka System Co., Ltd., VertScan 2.0, model: R5300 GL-Lite-AC) The surface morphology was observed using an observation mode = wave mode, surface correction = 4th order, filter = 530 nm white, objective lens = 50 ×, measurement area = 252.69 × 189.53 μm. The measurement was performed 5 times for one sample, and the average value was obtained. In addition, surface roughness SRa of a base film is surface roughness SRa of the surface which applies a mold release layer.

(3) Measurement of Pencil Hardness of Hard Coat Layer The pencil hardness of the hard coat layer when the transfer layer is a hard coat layer was measured in the following manner.

  After transferring the hard coat layer to the adherend according to the following transfer step (8), the pencil hardness of the hard coat layer surface is made according to JIS K5600-5-4 (1999), manufactured by Shinto Scientific Co., Ltd. Surface hardness tester (HEIDON; type 14DR). The load is 750 g and the speed is 30 mm / min.

(4) Measurement of Water Contact Angle of Antifouling Layer The water contact angle of the antifouling layer when the transfer layer was the antifouling layer was measured in the following manner.

  After transferring the antifouling layer to the adherend according to the following transfer step (8), the contact angle of water on the surface of the antifouling layer is analyzed with an automatic contact angle meter (DM-500) manufactured by Kyowa Interface Science Co., Ltd. It measured using FAMAS (version 3.34). Pure water was used for measurement, and the amount of dropped pure water was 2 microliters. It measured 5 times and adopted the average value of 3 points except maximum and minimum. The measurement environment is a temperature of 23 ° C. and a relative humidity of 55%.

(5) Measurement of refractive index of antireflective layer and high refractive index hard coat layer Coating formed by applying a composition for forming the antireflective layer and high refractive index hard coat layer on a silicon wafer The refractive index of 589 nm was measured for a thickness of about 2 μm under a temperature condition of 25 ° C. with a retardation measurement apparatus (manufactured by Nikon Corporation: NPDM-1000).

(6) Measurement of luminous reflectance of antireflective layer The luminous reflectance of the antireflective layer when the transfer layer is an antireflective layer was measured in the following manner.

  After transferring the antireflective layer to the adherend according to the following transfer step (8), a black adhesive tape is attached to the surface of the adherend opposite to the antireflective layer to form a measurement sample, as described below. The luminous reflectance was measured.

<Measurement of luminous reflectance>
Using a spectrophotometer (manufactured by Shimadzu Corporation, UV 3150PC), the reflectance (one-sided reflection) is calculated in the wavelength range of 380 to 780 nm at an incident angle of 5 degrees from the measurement surface, and the luminous reflectance (JIS Z8701-1999) The stimulation value Y of the defined reflex was determined. The spectral solid angle is measured with a spectrophotometer, and the reflectance (one-sided ray reflection) is calculated according to JIS Z8701-1999. The calculation formula is as follows.

T = K · ∫ S (λ) · y (λ) · R (λ) · dλ (where the integration interval is 380 to 780 nm)
T: single-sided light reflectance S (λ): standard light distribution used for color display y (λ): color matching function in XYZ display system R (λ): spectral solid angle reflectance.

(7) Evaluation of Coatability of Transfer Layer Each composition of the transfer layer was coated on the release layer of the release film in the same manner as in the following examples, and the coatability was evaluated based on the following criteria.
A (good); when a coating film having a uniform appearance and a good appearance is obtained B (good); a little coating unevenness is observed in the coating film, but when the appearance is within the specification C (not good); Or when strong coating unevenness is confirmed and the appearance is out of specification.

(8) Peelability evaluation of release film of transfer film In the process of transferring the transfer layer of a transfer film on which an adhesive layer, a hard coat layer, an antifouling layer or an antireflective layer is laminated as a transfer layer to an adherend The peelability between the release film and the transfer layer was evaluated in the following manner. The adherend was changed as follows according to the type of transfer layer.

<Adherend>
In the case where the transfer layer is an adhesive layer; a substrate in which a 25 μm-thick polyimide layer is laminated on a rough surface of a rolled copper foil (manufactured by JX Nippon Mining & Metals, thickness 35 μm). The transfer surface of the adhesive layer is the surface of a rolled copper foil.
· Transfer layer: hard coat layer, antifouling layer or antireflective layer; polyethylene terephthalate film with a thickness of 188 μm ("Lumirror (registered trademark)" U48, manufactured by Toray Industries, Inc.)
<Transfer process>
The transfer layer surface of the transfer film and the adherend were overlapped to prepare a test laminate. This laminate was inserted into a heating press (2ton vacuum heater press manufactured by Mikado Technos Co., Ltd. Model No. MKP-150TV-WH) and heat pressed at a press temperature of 160 ° C. and a press pressure of 2 MPa for 20 minutes. Then, after taking out a layered product and leaving it to stand at normal temperature for 1 hour, a release film was exfoliated from a layered product and the exfoliation nature was evaluated by the following standards.

<Evaluation of peelability>
A (good); when it can be peeled easily and smoothly B (if possible); when it can be peeled if a little force is applied C (not); if it can not be peeled off if a considerable force is applied [first transfer layer]
Hereinafter, a composition for obtaining a hard coat layer, an antifouling layer and an antireflective layer containing an adhesive layer containing an epoxy compound, and a compound having an ethylenically unsaturated group in the molecule is shown.

<Composition 1 for Adhesive Layer>
40 parts by mass of bisphenol A type epoxy resin ("Epiclon 840-S" manufactured by Dainippon Ink and Chemicals, Inc.) as an epoxy compound, 40 parts by mass of novolac type phenol resin ("PR-53647" manufactured by Sumitomo Bakelite Co., Ltd.) 20 parts by mass of phenoxy resin ("JL-9554" manufactured by Japan Epoxy Resins Co., Ltd.), 5 parts by mass of silica with an average particle diameter of 16 nm (manufactured by Nippon Aerosil Co., Ltd.), octyltriethoxysilane (Shin-Etsu Chemical Co., Ltd.) as a silane coupling agent 0.5 parts by mass of Industrial Co., Ltd. product, 20 parts by mass of salicylic acid, and 100 parts by mass of acetone were weighed and mixed and stirred.

<Adhesive layer composition 2>
As epoxy compound, triphenolmethane skeleton-containing polyfunctional solid epoxy (trade name “EP1032H60” 45 parts by mass manufactured by Japan Epoxy Resins Co., Ltd., bisphenol F liquid epoxy (trade name “YL 983 U” manufactured by Japan Epoxy Resins Co., Ltd.) 15 parts by mass, 5 parts by mass of a flexible epoxy resin (trade name "YL7175" manufactured by Japan Epoxy Resins Co., Ltd.), 2,4-diamino-6- [2'-methylimidazolyl- (1 ') as a curing agent 4 parts by mass of 2-ethyl-s-triazine isocyanuric acid adduct (trade name "2MAOK-PW" manufactured by Shikoku Kasei Co., Ltd.), 4 parts by mass of 2-methyl glutaric acid, silica having an average particle diameter of 100 nm 10 parts by mass of Admatex's trade name “SE1050”, methacryl surface-treated nano-silicon having an average particle diameter of 50 nm (Trade name "YA050C-SM" (trade name of Admatex Co., Ltd.)) 55 parts by mass, organic resin particles (trade name "EXL-2655" manufactured by Rohm and Haas Japan Ltd .: core-shell type organic fine particles) 10 parts by mass 2 parts by mass of a glycidyl silane coupling agent (trade name “SH6040” manufactured by Toray Dow Corning Co., Ltd.) and methyl ethyl ketone were charged so as to have a solid concentration of 60 mass%, and stirred for 30 minutes with a bead mill. 20 parts by mass (trade name “ZX-1356-2” manufactured by Tohto Kasei Co., Ltd.) was added, and the mixture was again stirred for 30 minutes with a bead mill to prepare.

<Composition 3 for adhesive layer>
100 parts by mass of an epoxy compound (manufactured by Japan Epoxy Resins Co., Ltd., trade name "Epikote 828EL"), 40 as a thermoplastic resin carboxylated NBR (trade name "" NIPOL (registered trademark) 1072 ") manufactured by Nippon Zeon Co., Ltd. A mass part and 25 mass parts of 4, 4'- diaminodiphenyl sulfone as a hardening agent were dissolved and dispersed in methyl ethyl ketone, and it prepared so that solid content concentration might be 30 mass%.

<Composition 1 for Hard Coat Layer>
58 parts by mass of dipentaerythritol hexaacrylate (trade name "Light Acrylate DPE-6A" manufactured by Kyoeisha Chemical Co., Ltd.) as a compound having an ethylenically unsaturated group in the molecule, and an ethylenically unsaturated group and a urethane bond in the molecule 37 parts by mass of a urethane acrylate oligomer (trade name "UN-901T" manufactured by KONAMI KOGYO CO., LTD.), A photopolymerization initiator ("IRGACURE (registered trademark)" 184 manufactured by Ciba Specialty Chemicals Inc.) 5 parts by mass was dissolved in methyl isobutyl ketone to prepare a coating liquid having a solid content concentration of 20% by mass.

<Composition 2 for Hard Coat Layer>
20 parts by mass of dipentaerythritol hexaacrylate (trade name "Light Acrylate DPE-6A" manufactured by Kyoeisha Chemical Co., Ltd.) as a compound having an ethylenically unsaturated group in the molecule; 140 parts by mass of a compound (UA) having a saturated group and a urethane bond, 5 parts by mass of a photopolymerization initiator (Ciba Specialty Chemicals Co., Ltd. “IRGACURE (registered trademark)” 907), solid content of the following reactive silica 5 mass% was mixed by mass ratio (ratio to the total solid of the said composition), and it diluted with methyl ethyl ketone, and prepared so that solid content concentration might be 20 mass%.

<Synthesis of Compound (UA)>
In a four-necked flask, 3180 parts by mass of bisphenol F diepoxy resin (trade name "Epototh YDF-8170C" manufactured by Toto Kasei Co., Ltd.), 1440 parts by mass of acrylic acid, and hydroquinone monomethyl ether as a polymerization inhibitor 4. 6 parts by mass, 23 parts by mass of dimethylaminoethyl methacrylate (trade name “Acryester DM” manufactured by Mitsubishi Rayon Co., Ltd.) as a synthesis catalyst, charged, heated to 95 ° C. with stirring, and maintained at 95 ° C. The reaction continued for 14 hours. When the acid value became 1 mg KOH / g or less, the internal temperature was cooled to 60 ° C. to obtain an epoxy (meth) acrylate compound.

  Next, 298 parts by mass of the above-mentioned epoxy (meth) acrylate compound and 711.3 parts by mass of ethyl acetate were charged into a four-necked flask, and the mixture was heated to an internal temperature of 60 ° C. 0.21 parts by mass of di-n-butyltin dilaurate as a synthesis catalyst and 199 parts by mass of methylcyclohexylene diisocyanate (trade name "Takenate 600" manufactured by Mitsui Chemicals Polyurethanes Co., Ltd.) for 1 hour while stirring It dripped over. After completion of the addition, the reaction is continued for 2 hours, followed by 27.3 parts by mass of diethylene glycol (reagent manufactured by Wako Pure Chemical Industries, Ltd., trade name "diethylene glycol"; molecular weight 106), pentaerythritol tetraacrylate (Toa Synthesis (stock A mixture of 187 parts by mass of a trade name "ALONIX M-306" manufactured by A.M.) was added dropwise over 1 hour. After the addition, the reaction was continued for 5 hours to obtain a urethane (meth) acrylate compound having a weight average molecular weight of 19,800.

<Reactive silica>
150 parts by mass of colloidal silica ("Organosilica sol (registered trademark)" MEK-ST manufactured by Nissan Chemical Industries, Ltd., solid content 30% by mass, methyl ethyl ketone 70% by mass), 3-methacryloyloxypropyltrimethoxysilane (Shin-Etsu silicon) 13.7 parts by mass of trade name "KBM-503" (trade name) and 1.7 parts by mass of 10 mass% formic acid aqueous solution were mixed, and stirred at 70 ° C for 1 hour to obtain reactive silica .

<Composition 3 for Hard Coat Layer>
An ultraviolet curable resin coating solution ("UV-7550B" from Nippon Gohsei Kagaku Co., Ltd.) containing a compound having an ethylenically unsaturated group and a urethane bond in its molecule, and a solid content concentration of 20% by mass with methyl ethyl ketone As diluted.

<Composition 4 for Hard Coat Layer>
An ultraviolet-curable hard coat paint (trade name “Forseed No. 301C” manufactured by China Paint Co., Ltd.) containing a compound having an ethylenically unsaturated group in its molecule was adjusted to a solid content concentration of 30 mass% with methyl ethyl ketone .

<Composition for antifouling layer 4>
A UV curable hard coat paint containing a compound having an ethylenic unsaturated group and a fluorine atom in the molecule (trade name “Porceed No. 421C” of China Paint Co., Ltd.) made of methyl ethyl ketone to a solid content concentration of 30 mass% Prepared.

<Composition 1 for Antireflection Layer>
57 parts by mass of dipentaerythritol hexaacrylate (trade name "Light Acrylate DPE-6A" manufactured by Kyoeisha Chemical Co., Ltd.) as a compound having an ethylenically unsaturated group in the molecule, isopropyl alcohol dispersion of hollow silica particles (JV catalyst Kasei Co., Ltd. product: solid content concentration of 20% by mass, average particle diameter 60 nm) 40 parts by mass in terms of solid content, photopolymerization initiator (Ciba Specialty Chemicals Co., Ltd. product “IRGACURE (registered trademark)” 184 3 parts by weight was prepared by dispersing or dissolving in methyl ethyl ketone. The refractive index of this composition was 1.37.

[Second transfer layer]
<Composition for adhesive layer>
A hot melt adhesive ("Aronmelt (registered trademark)" PPET-1303S manufactured by Toagosei Co., Ltd.) was used.

<Composition for high refractive index hard coat layer>
10 parts by mass of dipentaerythritol hexaacrylate (trade name “Light Acrylate DPE-6A” manufactured by Kyoeisha Chemical Co., Ltd.) and 37 parts by mass of urethane acrylate oligomer (trade name “UN-901T” manufactured by Kegami Kogyo Co., Ltd.) It was prepared by dispersing or dissolving 60 parts by mass of zirconium oxide and 3 parts by mass of a photopolymerization initiator (“IRGACURE (registered trademark)” 184 manufactured by Ciba Specialty Chemicals Co., Ltd.) in an organic solvent. The refractive index of this composition was 1.70.

[Base film]
The following polyester film and polyimide film were prepared as a base film which comprises a release film.

<Polyester film 1>
A polyester film ("Lumirror (registered trademark)" R75X) manufactured by Toray Industries, Inc. was prepared. The polyester film had a thickness of 25 μm and a surface roughness SRa of 25 nm.

<Polyester film 2>
A polyester film ("Lumirror (registered trademark)" S10) manufactured by Toray Industries, Inc. was prepared. The polyester film had a thickness of 100 μm and a surface roughness SRa of 25 nm.

<Polyimide film 1>
A polyimide film ("Kapton (registered trademark)" H100) manufactured by Toray DuPont Co., Ltd. was prepared. The polyimide film had a thickness of 25 μm and a surface roughness SRa of 50 nm.

Example 1
A release film was produced in the following manner.

The following composition for an anchor layer is coated by a gravure coater on one side of the polyester film 1 and dried and heated at 120 ° C, and subsequently, the composition p1 for a release layer described below is coated by a gravure coater, 100 ° C After pre-drying, heat-dried at 160 ° C. to laminate the anchor layer and the release layer. The thickness of the anchor layer was 50 nm, and the thickness of the release layer was 300 nm. The surface free energy of the release layer was 31 mJ / m ² , and the surface roughness SRa of the release layer was 20 nm.

<Composition for anchor layer>
5 parts by mass of 3-glycidoxypropyltrimethoxysilane (trade name "BY24-846B" manufactured by Toray Dow Corning; content: 98% by mass), 3-methacryloxypropyltrimethoxysilane (Toray Dow Corning) Co., Ltd. trade name "XIAMETER" OFS-6030 SILANE (content: 99% by mass) 1 part by mass, bis (ethylacetoacetate) (2,4-pentanedionate) aluminum (Toray Dow Corning (Australia) as aluminum chelate It prepared by adding and mixing 2 mass parts of brand names "BY24-846E"; content amount of 38 mass%) manufactured by Co., Ltd. in a mixed solvent of 50 mass parts of toluene and 50 mass parts of isopropyl alcohol.

<Composition for Release Layer p1>
-Silicone modified alkyd resin; 100 parts by mass of "X-62-9022" (Silicone modification rate is 1% by mass, containing a melamine crosslinking agent) manufactured by Shin-Etsu Chemical Co., Ltd.-Acid catalyst; p-toluenesulfonic acid (Shin-Etsu Chemical Co., Ltd. trade name "CAT-PC-80") 1.3 parts by mass · Solvent; 245 parts by mass of toluene, 165 parts by mass of methyl ethyl ketone [Example 2]
A release film was produced in the same manner as in Example 1 except that the composition for release layer was changed to the following composition p2. The surface free energy of the release layer was 28 mJ / m ² , and the surface roughness SRa of the release layer was 20 nm.

<Composition for Release Layer p2>
· Silicone modified alkyd resin; 100 parts by mass, trade name "KS-881" (containing 5% by mass silicone modification, containing a melamine crosslinking agent) manufactured by Shin-Etsu Chemical Co., Ltd. · Acid catalyst; p-toluenesulfonic acid (Shin-Etsu) 1.3 parts by mass of "CAT-PC-80" (trade name, manufactured by Chemical Industry Co., Ltd.), 240 parts by mass of a solvent, 240 parts by mass of toluene, and 160 parts by mass of methyl ethyl ketone [Example 3]
A release film was produced in the same manner as in Example 1 except that the composition for release layer was changed to the following composition p3. The surface free energy of the release layer was 25 mJ / m ² , and the surface roughness SRa of the release layer was 20 nm.

<Composition for Release Layer p3>
-Silicone modified alkyd resin; 100 parts by mass of "KS-883" (10% by mass silicone modification rate, containing a melamine crosslinking agent), trade name of Shin-Etsu Chemical Co., Ltd.-Acid catalyst; p-toluenesulfonic acid (Shin-Etsu) 1.3 parts by mass of "CAT-PC-80" (trade name, manufactured by Chemical Industry Co., Ltd.), 240 parts by mass of a solvent, 240 parts by mass of toluene, and 160 parts by mass of methyl ethyl ketone [Example 4]
A release film was produced in the same manner as in Example 1 except that the composition for release layer was changed to the following composition p4. The surface free energy of the release layer was 21 mJ / m ² , and the surface roughness SRa of the release layer was 20 nm.

<Composition for Release Layer p4>
-Silicone modified alkyd resin; 100 parts by mass, trade name "KS-882" (containing 20% by mass silicone modification, containing a melamine crosslinking agent) manufactured by Shin-Etsu Chemical Co., Ltd.-Acid catalyst; p-toluenesulfonic acid (Shin-Etsu) 1.3 parts by mass of "CAT-PC-80" (trade name, manufactured by Chemical Industry Co., Ltd.), 240 parts by mass of a solvent, 240 parts by mass of toluene, and 160 parts by mass of methyl ethyl ketone [Example 5]
A release film was produced in the same manner as in Example 1 except that the composition for release layer was changed to the following composition p5. The surface free energy of the release layer was 29 mJ / m ² , and the surface roughness SRa of the release layer was 20 nm.

<Composition for Release Layer p5>
-Silicone modified alkyd resin; 100 mass parts of "Tes fine 309" (Silicone modified alkyd resin / melamine crosslinking agent (mass ratio) = 65/35, silicone modification ratio 3 mass%) manufactured by Hitachi Chemical Co., Ltd. Acid catalyst: 1.3 parts by mass of p-toluenesulfonic acid (trade name "CAT-PC-80" manufactured by Shin-Etsu Chemical Co., Ltd.) Solvent: 420 parts by mass of toluene, 280 parts by mass of methyl ethyl ketone Example 6]
A release film was produced in the same manner as in Example 2 except that polyester film 1 was changed to polyester film 2 in Example 2. The surface free energy of the release layer was 28 mJ / m ² , and the surface roughness SRa of the release layer was 20 nm.

[Example 7]
A release film was produced in the same manner as in Example 2 except that polyester film 1 was changed to polyimide film 1 in Example 2. The surface free energy of the release layer was 28 mJ / m ² , and the surface roughness SRa of the release layer was 40 nm.

Comparative Example 1
The following composition p6 for release layer was applied by a gravure coater on one side of the polyester film 1, and after preliminary drying at 100 ° C., it was dried by heating at 160 ° C. to laminate a release layer. The thickness of this release layer was 300 nm. The surface free energy of the release layer was 19 mJ / m ² , and the surface roughness SRa of the release layer was 20 nm.

<Composition for Release Layer p6>
40 parts by mass of an addition reaction type curable silicone resin (trade name "LTC 750A" manufactured by Toray Dow Corning Co., Ltd.) and 0.4 parts by mass of PL-50T (manufactured by Shin-Etsu Chemical Co., Ltd.) as a curing agent 500 parts by mass of toluene and 500 parts by mass of n-heptane were mixed.

Comparative Example 2
A release film was produced in the same manner as in Comparative Example 1 except that the composition for release layer was changed to the following composition p7. The surface free energy of the release layer was 50 mJ / m ² , and the surface roughness SRa of the release layer was 20 nm.

<Composition for Release Layer p7>
20 parts by mass of a melamine-based resin (trade name "RP-50" manufactured by Sanba Laboratories Co., Ltd.), 4 parts by mass of a curing agent ("Plus Coat (registered trademark)" DEP clear manufactured by Washin Chemical Industry Co., Ltd.) Were mixed with 50 parts by mass of toluene and 50 parts by mass of cyclohexanone.

<Evaluation>
The evaluation results of the release film obtained above are shown in Table 1.

[Examples 11 to 17 and Comparative Examples 11 to 12]
A transfer film in which an adhesive layer was laminated as a transfer layer was produced in the following manner.

<Lamination of adhesive layer>
The adhesive layer compositions 1 to 3 containing an epoxy compound on the release layer of the release film prepared in Examples 1 to 7 and Comparative Examples 1 to 2 have a thickness after drying of 25 μm. It applied using the applicator, dried at 150 degreeC, and formed the adhesive layer.

<Evaluation>
The evaluation results of the transfer film obtained above are shown in Table 2.

[Examples 21 to 27 and Comparative Examples 21 to 22]
A hard coat layer as a first transfer layer and an adhesive layer as a second transfer layer are laminated in this order on the release layer of the release film prepared in Examples 1 to 7 and Comparative Examples 1 to 2 to prepare a transfer film. did.

<Lamination of Hard Coat Layer (First Transfer Layer)>
Hard coat layer compositions 1 to 4 are applied using a wire bar so that the thickness after drying and curing is 7 μm, dried at 90 ° C., irradiated with 500 mJ / cm ^{2 of} ultraviolet light, and cured to give a hard coat Layers were stacked.

<Lamination of adhesive layer (second transfer layer)>
A hot melt type adhesive layer ("Aronmelt (registered trademark)" PPET-1303S manufactured by Toagosei Co., Ltd.) was laminated with a wire bar so that the dry thickness was 1.5 μm.

<Evaluation>
The evaluation results of the transfer film obtained above are shown in Table 3.

[Examples 31 to 37 and Comparative Examples 31 to 32]
An antifouling layer as a first transfer layer and an adhesive layer as a second transfer layer are laminated in this order on the release layer of the release film produced in Examples 1 to 7 and Comparative Examples 1 and 2 to produce a transfer film. did.

<Lamination of antifouling layer (first transfer layer)>
The composition 1 for antifouling layer is applied using a wire bar so that the thickness after drying and curing becomes 7 μm, dried at 90 ° C., irradiated with 500 mJ / cm ^{2 of} ultraviolet rays and cured to form a hard coat layer Stacked.

<Lamination of adhesive layer (second transfer layer)>
A hot melt adhesive ("Aronmelt (registered trademark)" PPET-1303S manufactured by Toagosei Co., Ltd.) was laminated with a wire bar to a dry thickness of 1.5 μm.

<Evaluation>
The evaluation results of the transfer film obtained above are shown in Table 4.

[Examples 41 to 47 and Comparative Examples 41 to 42]
On the release layer of the release film produced in Examples 1 to 7 and Comparative Examples 1 and 2. An antireflective layer as a first transfer layer and a high refractive index hard coat layer and an adhesive layer as a second transfer layer were laminated in this order to prepare a transfer film.

<Lamination of Antireflection Layer (First Transfer Layer)>
The composition for antireflective layer 1 is applied using a wire bar so that the thickness after drying and curing becomes 0.1 μm, dried at 90 ° C., irradiated with 300 mJ / cm ^{2 of} ultraviolet light, and cured to prevent antireflective Layers were stacked.

<Lamination of High Refractive Index Hard Coat Layer (Second Transfer Layer)>
The composition for high refractive index hard coat layer is applied using a wire bar to a dry and cured thickness of 5 μm, dried at 90 ° C, irradiated with 500 mJ / cm ^{2 of} ultraviolet light and cured to achieve high refractive index Rate hard coat layer was laminated.

<Lamination of adhesive layer (second transfer layer)>
A hot melt adhesive ("Aronmelt (registered trademark)" PPET-1303S manufactured by Toagosei Co., Ltd.) was laminated with a wire bar to a dry thickness of 1.5 μm.
<Evaluation>
The evaluation results of the transfer film obtained above are shown in Table 5.

Claims (9)

  It is a release film used for a transfer film on which a transfer layer containing at least one selected from the group consisting of an epoxy compound and a compound having an ethylenically unsaturated group in the molecule is laminated, which is a silicone film on a substrate film A release film for transfer film, comprising a release layer containing a modified alkyd resin.   The release film for transfer film according to claim 1, wherein the transfer layer is at least one layer selected from the group consisting of an adhesive layer, a hard coat layer, an antifouling layer and an antireflective layer.   The release film for transfer film according to claim 1 or 2, wherein the content of the silicone-modified alkyd resin in the release layer is 40% by mass or more based on 100% by mass of the total solid content of the release layer.   The release film for transfer film according to any one of claims 1 to 3, wherein the release layer further contains a melamine crosslinking agent.   The release film for transfer films according to any one of claims 1 to 4, wherein an anchor layer is disposed between the base film and the release layer.   The release film for transfer film according to claim 5, wherein the anchor layer contains a silane compound and a metal complex having an organic ligand.   The release film for transfer film according to claim 6, wherein the central metal of the metal complex having the organic ligand is at least one selected from the group consisting of aluminum, titanium and zirconium.   A transfer comprising at least one selected from the group consisting of an epoxy compound and a compound having an ethylenically unsaturated group in the molecule on the release layer of the release film for transfer film according to any one of claims 1 to 7. Transfer film in which layers are laminated.   The transfer film according to claim 8, wherein the transfer layer is at least one layer selected from the group consisting of an adhesive layer, a hard coat layer, an antifouling layer and an antireflective layer.