JP6934141B2 - Release film for transfer film and transfer film - Google Patents

Description

The present invention relates to a release film and a transfer film used for a transfer film in which transfer layers such as an adhesive layer and a hard coat layer are laminated.

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

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

Further, a transfer foil (transfer film) having a release layer and a hard coat layer on the base material in this order has been proposed (for example, Patent Documents 3 and 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.

Further, a transfer film in which an antifouling and curing layer is laminated on a base film has been proposed (for example, Patent Document 5). The antifouling hardened layer contains a fluorine-containing polymerizable monomer.

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

Japanese Unexamined Patent Publication No. 2005-39247 JP-A-2010-109383 Japanese Unexamined Patent Publication No. 2013-185078 JP-A-2017-65017 International Publication No. 2011/0433361 Japanese Unexamined Patent Publication No. 2008-151930

The transfer layer in the above transfer film, that is, the epoxy adhesive layer, the hard coat layer, the antifouling layer, and the antireflection layer is an epoxy compound or a (meth) acrylate compound (a compound having an ethylenically unsaturated group in the molecule). It is formed by applying a thermosetting composition or an active energy ray-curable composition containing the above on a release film. At this time, coatability is required so that the composition can be uniformly coated on the release film.

Further, when the transfer layer of the transfer film is transferred to the adherend, the release film can be peeled off relatively easily (smoothly).

In general, the coatability of the transfer layer on the release film and the peelability are contradictory properties, and the prior art described in Patent Documents 1 to 6 described above can sufficiently satisfy the coatability and the peelability at the same time. It wasn't a thing.

Therefore, an object of the present invention is a release film for a transfer film having good coatability and peelability 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. Is to provide. Another object of the present invention is to provide a transfer film on the release film of the present invention, which comprises 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. To provide.

The above object of the present invention has been achieved by the following invention.
[1] A release film used for a transfer film in 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 is on a base film. A release film for a transfer film provided with a release layer containing a silicone-modified alkyd resin.
[2] The release film for a 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 antireflection layer.
[3] The release for a 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 with respect to 100% by mass of the total solid content of the release layer. Mold film.
[4] The release film for a transfer film according to any one of [1] to [3], wherein the release layer further contains a melamine cross-linking agent.
[5] The release film for a transfer film according to any one of [1] to [4], wherein an anchor layer is arranged between the base film and the release layer.
[6] The release film for a 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 a transfer film according to [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.
[8] At least 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 [1] to [7]. A transfer film in which transfer layers containing one type are 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 antireflection layer.

The release film for a transfer film of the present invention has good coating properties 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. A uniform transfer layer having a good appearance can be obtained. Further, since the release film for transfer film of the present invention has good peelability from the transfer layer, it can be peeled off relatively easily (smoothly) when the transfer layer is transferred to an adherend.

Further, the transfer film in which the transfer layer is laminated on the release film for transfer film of the present invention has a uniform transfer layer and a good appearance, and is a release film when the transfer layer is transferred to an adherend. Good peelability.

The release film for a transfer film of the present invention is a release film for transferring the transfer layer of the transfer film in which the transfer layer is temporarily laminated on the release film to the adherend. That is, it is a release film for a transfer film used for a transfer film in which transfer layers are laminated. Hereinafter, the release film for transfer film may be simply referred to as "release film".

The release film of the present invention includes a release layer containing a silicone-modified alkyd resin on a base film. A transfer film 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 via an adhesive layer, etc., and if necessary, it is heated and pressed to adhere to the adherend, and then the release film is peeled off so that the transfer layer becomes an adherend. Transfer adhered. In the present invention, "containing at least one selected from the group consisting of an epoxy compound and a compound having an ethylenically unsaturated group in the molecule" means that the epoxy compound and / or the ethylenically unsaturated group is contained 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. Including the case of having a structure.

The release layer of the release film of the present invention has good coating properties 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. A uniform transfer layer having a good appearance can be obtained. Further, since the release layer of the release film of the present invention has good releasability from the transfer layer, the release film can be smoothly peeled off after the transfer layer is brought into 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 a circuit board, a multilayer printed wiring board, and a plastic resin molded product. 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, etc. Examples include automobile interior parts (instrument panels, consource boxes, door trims, etc.).

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

In the present invention, the alkyd resin refers to a resin modified by further reacting a fatty oil or a fatty acid with a chemical structure having a condensate 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 and neopentyl glycol, and glycerin, trimethylolethane, trimethylpropane and the like. Hydrate alcohols, diglycerin, triglycerin, pentaerythritol, dipentaerythritol, mannit, sorbit and other tetrahydric or higher alcohols can be mentioned. These may be used individually by 1 type, and may be used in combination of 2 or more type.

Examples of the polybasic acid include saturated polybasic acids such as phthalic anhydride, terephthalic acid, succinic acid, adipic acid and sebacic acid, maleic anhydride, maleic anhydride, fumaric acid, itaconic acid and citraconic anhydride. Other polybasic acids such as unsaturated polybasic acid, cyclopentadiene-maleic anhydride adduct, terpene-maleic anhydride adduct, rosin-maleic anhydride adduct can be mentioned. These may be used individually by 1 type, and may be used in combination of 2 or more type.

Examples of the above-mentioned fatty acids and fatty acids include fatty oils such as soybean oil, flaxseed oil, millet oil, castor oil, dehydrated castor oil and palm oil, and these fatty acids, stearic acid, oleic acid, linoleic acid, linoleic acid and eleo. Examples thereof include oils and fats such as stearic acid, ricinoleic acid and dehydrated ricinoleic acid, and oil and fat fatty acids. These may be used individually by 1 type, and may be used in combination of 2 or more type.

As the silicone modifier for obtaining the silicone-modified alkyd resin, a compound having an alkoxysilyl group or a silanol group can be used. Specific examples thereof include organopolysiloxane having an organic group such as dimethylpolysiloxane, in which a part of the organic group is replaced with a phenyl group, an ethyl group, an isopropyl group, a hexyl group, a cyclohexyl group, a hydroxyl group, a vinyl group or the like. It may have been done. These may be used individually by 1 type, and may be used in combination of 2 or more type.

The silicone modification rate of 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 exhibiting good coatability and good peelability of the transfer layer. 10% by mass is more preferable, and 2 to 5% by mass is particularly preferable.

Silicone-modified alkyd resins are commercially available and can be used. Commercially available products include Shin-Etsu Chemical Co., Ltd. trade names KS-881, KS-882, KS-883, X-62-9022, X-62-9827, X-62-950A, Toray Dow Corning Co., Ltd. ), Trade names SR2107, SR2114, Toshiba Silicone Co., Ltd., trade name TSR180, Hitachi Chemical Co., Ltd., trade names Tessfine 309, 319, TA31-209E, etc.

The release layer preferably further contains a cross-linking agent. When the release layer contains a cross-linking agent, the coatability and peelability of the transfer layer are further improved.

Examples of the cross-linking agent include an epoxy cross-linking agent, an isocyanate cross-linking agent, an oxazoline cross-linking agent, a carbodiimide cross-linking agent, a melamine cross-linking agent and the like. These may be used individually by 1 type, and may be used in combination of 2 or more type.

Among the above, a melamine cross-linking agent is particularly preferable. By using the melamine cross-linking agent, the coatability and the peelability are further improved.

Examples of the epoxy cross-linking agent include ethylene glycol diglycidyl ether, glycerol polyglycidyl ether, and polybutadiene diglycidyl ether.

Examples of the isocyanate cross-linking agent include hexamethylene diisocyanate, isophorone diisocyanate, tolylene diisocyanate, methylene diphenyl diisocyanate and the like.

Examples of the oxazoline cross-linking agent include 2,2'-bis (2-oxazoline), 2,2'-ethylene-bis (4,4'-dimethyl-2-oxazoline), and 2,2'-p-phenylene-. Examples thereof include compounds having an oxazoline group such as bis (2-oxazoline) and bis (2-oxazoline cyclohexane) sulfide, and oxazoline group-containing polymers.

Examples of the carbodiimide cross-linking agent include carbodiimides such as p-phenylene-bis (2,6-xysilylcarbodiimide), tetramethylene-bis (t-butylcarbodiimide), and cyclohexane-1,4-bis (methylene-t-butylcarbodiimide). Examples thereof include a compound having a group and polycarbodiimide which is a polymer having a carbodiimide group.

The melamine compound used as a melamine cross-linking agent is various to the amino group of so-called melamine [1,3,5-triazine-2,4,6-triamine] in which an amino group is bonded to each of the three carbon atoms of the triazine ring. It is a general term for compounds that have undergone the above-mentioned modification, and includes those in which a plurality of triazine rings are condensed. As the type of modification, a methylolated melamine compound in which at least one of the hydrogen atoms of the three amino groups is methylolated is preferable, and the methylol group of the methylolated melamine compound is partially or partially composed of a lower alcohol having 1 to 4 carbon atoms. Fully etherified alkyl etherified melamine compounds are preferred.

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

A commercially available product can be used as the melamine cross-linking agent. Examples of commercially available products include "Super Beccamin (registered trademark)" J-820-60, J-821-60, J-1090-65, J-110-60, and J of DIC Co., Ltd. -117-60, J-127-60, J-166-60B, J-105-60, G840, G821, Mitsui Chemicals Co., Ltd. "Uban (registered trademark)" 20SB, 20SE60, 21R, 22R, 122, 125, 128, 220, 225, 228, 28-60, 2020, 60R, 62, 62E, 360, 165, 166- 60, 169, 2061, Sumitomo Chemicals Co., Ltd. "Sumimar (registered trademark)" M-100, M-40S, M-55, M-66B, Nippon Cytec Industries "Symel (registered trademark)" "303, 325, 327, 350, 370, 235, 202, 238, 254, 272, 1130, Sanwa Chemicals Co., Ltd." Nicarak (registered trademark) "MS17, same Examples thereof include MX15, MX430, MX600, Vancemin SM-975 and SM-960 of Harima Kasei Co., Ltd., and "Melan (registered trademark)" 265 and 2650L of Hitachi Kasei Co., Ltd.

Among the commercially available products of the silicone-modified alkyd resin described above, there are some that contain a melamine cross-linking agent or the like as a cross-linking agent for curing the silicone-modified alkyd resin. When such a commercially available product is used, it is not always necessary to newly add the above-mentioned cross-linking 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. Examples of the acid catalyst include sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, p-toluenesulfonic acid and the like. 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 with respect to 100% by mass of the total solid content of the release layer from the viewpoint of improving the coatability and peelability of the transfer layer. , 50% by mass or more is more preferable, and 60% by mass or more is particularly preferable. On the other hand, if the content of the silicone-modified alkyd resin becomes too large, the strength (hardness) of the release layer may decrease, and the solvent resistance and heat resistance may decrease. Therefore, the content of the silicone-modified alkyd resin is 97. It is preferably 9% by mass or less, more preferably 95% by mass or less, and particularly preferably 90% by mass or less.

When the release layer contains a cross-linking agent, the content of the cross-linking agent is 3% by mass or more with respect to 100% by mass of the total solid content of the release layer from the viewpoint of improving the coatability and peelability of the transfer layer. Is preferable, 5% by mass or more is more preferable, and 10% by mass or more is particularly preferable. On the other hand, if the content of the cross-linking agent is too large, the peelability may decrease. Therefore, the content of the cross-linking agent is preferably 60% by mass or less, more preferably 50% by mass or less, and 40% by mass or less. Especially preferable.

When the release layer contains an acid catalyst, the content of the acid catalyst is 0.1 to 10% by mass with respect to 100% by mass of the total solid content of the release layer from the viewpoint of improving coatability and peelability. % Is preferable, 0.3 to 5% by mass is more preferable, and 0.5 to 3% by mass is particularly preferable.

The release layer can further contain a binder resin. Examples of such a binder resin include polyurethane resin, acrylic resin, polyester resin and the like.

The release layer is preferably formed by applying a composition containing a silicone-modified alkyd resin onto a base film and heat-curing it. 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 cross-linking agent, and more preferably contains an acid catalyst. In addition, the composition can contain a binder resin.

The conditions (heating temperature, time) for curing the composition are not particularly limited, but the heating temperature is preferably 70 ° C. or higher, more preferably 100 ° C. or higher, and particularly preferably 150 ° C. or higher. 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, for example, by a wet coating method. Examples of the wet coating method include a reverse coating method, a spray coating method, a bar coating method, a gravure coating method, a rod coating method, a die coating method, a spin coating method, an extrusion coating method, a curtain coating method and the like.

The thickness of the release layer is preferably 30 to 1000 nm, more preferably 50 to 600 nm, further preferably 70 to 500 nm, and particularly preferably 100 to 400 nm.

Surface free energy of the release layer is preferably 20~35mJ / ^{m 2,} more preferably ^{21~32mJ / m 2, 22~30mJ / m} 2 is particularly preferred. When the surface free energy of the release layer is within the above range, the coatability and peelability 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 further, the surface free energy can be easily adjusted to the above range by containing a cross-linking agent.

Here, the surface free energy can be measured using a contact angle meter, for example, "Drop Master DM501" of 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 peelability 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 ensuring the slipperiness and winding of the release film or transfer film.

As a method of controlling the surface roughness SRa of the release layer to 50 nm or less, a method of using a base film having a surface roughness SRa of the surface on which the release layer is laminated is 60 nm or less is preferable. Further, the release layer preferably does not contain particles, or if it contains particles, it is preferably in a small amount. When the release layer contains particles, the content of the particles is preferably 3.0% by mass or less, preferably 1.0% by mass or less, based on 100% by mass of the total solid content of the release layer. Is more preferable, and 0.5% by mass or less is particularly preferable.

Here, the surface roughness SRa can be measured using an optical interference type microscope, for example, "VertScan" manufactured by Ryoka System Co., Ltd.

[Base film]
The base film used for the release film of the present invention is not particularly limited, and 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 and polyethylene film, cellulose film such as diacetyl cellulose film and triacetyl cellulose film, polysulfone film, polyether ether ketone. Examples thereof include films, polyether sulfone films, polyphenylene sulfide films, polyetherimide films, polyimide films, polyamide films, acrylic films, cyclic olefin films, and polycarbonate films.

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

When a polyester film is used as the base film, a polyester film having a three-layer laminated structure is preferable from the viewpoint of controlling the surface roughness SRa of the base film. Examples of the three-layer laminated structure include A layer / B layer / A layer or A layer / B layer / C layer. Here, the A layer, the B layer, and the C layer have different compositions.

In the above three-layer structure, the A layer or the C layer 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 A layer or the C layer.

The surface roughness SRa on the side where the release layer of the base film is laminated is preferably 60 nm or less, more preferably 50 nm or less, and particularly preferably 30 nm or less. Further, 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 ensuring the slipperiness and winding of the release film.

From the viewpoint of simplifying the production equipment and improving the productivity, a polyester film having a three-layer laminated structure of A layer / B layer / A layer is preferably used.

The thickness of the base film is preferably 10 to 200 μm, more preferably 15 to 150 μm, and particularly preferably 20 to 100 μm.

[Anchor layer]
It is preferable to arrange an anchor layer between the base film and the release layer to improve the adhesion between the base film and the release layer.

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

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

Si (X) a (Y) b (R) c ... General formula (1)
(In the formula, X represents a group to which one selected from the group consisting of a glycidoxy group, a mercapto group, a (meth) acryloxy group and an amino group is bonded to an alkylene group, an alkenyl group, a vinyl group or a haloalkyl group, and Y represents a haloalkyl group. Represents a hydrolyzable group, R represents a hydrocarbon group, a represents 0 or 1, b represents 2 or 3, c represents 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 butanoxim group, a ketoxim group, an amino group and the like, and these may be used alone or in combination of two or more. Can be done. Of these, the methoxy group and the ethoxy group 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, a methyl group, an ethyl group, a propyl group, a hexyl group, an octyl group, a decyl group, a phenyl group, and the like. Cyclohexyl groups and the like can be mentioned.

Specific examples of the silane compound represented by the general formula (1) include methyltrimethoxysilane, methyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, n-propyltrimethoxysilane, and n-propyltriethoxysilane. , Hexyltrimethoxysilane, hexyltriethoxysilane, cyclohexyltrimethoxysilane, octyltriethoxysilane, decyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane , 3-Mercaptopropyltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxy Propyltrimethoxysilane, 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-glycidoxypropyltrimethoxycisilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyl Examples thereof include diethoxysilane, 3-glycidoxypropylmethyldiisopropenoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinylmethyldimethoxysilane and the like. ..

As the central metal of the metal complex having an organic ligand, at least one selected from the group consisting of aluminum, zirconium and titanium is preferable. Of these, aluminum and zirconium are preferable, and aluminum is particularly preferable. Further, as the metal complex having an organic ligand, a chelate compound having the above-mentioned central metal is preferable, and an aluminum chelate compound is particularly preferable.

Specific examples of the metal complex having an organic ligand with aluminum as the central metal include bis (ethylacetoacetate) (2,4-pentandionate) aluminum, aluminum tris (acetylacetoneate), and aluminum tris. (Ethylacetacetate), aluminum monoacetylacetonate bis (ethylacetate acetate), aluminum-di-n-butoxide-monoethylacetate, aluminum-di-isopropoxide-monomethylacetate, and the like.

Specific examples of the metal complex having an organic ligand with zirconium as the central metal include, for example, zirconium acetate, zirconium normal propylate, zirconium normal butyrate, zirconium tetraacetylacetonate, zirconium monoacetylacetonate, and zirconium bis. Examples include acetylacetonate.

Specific examples of the metal complex having an organic ligand with titanium as the central metal include titanium such as tetranormal butyl titanate, tetraisopropyl titanate, butyl titanate dimer, tetra (2-ethylhexyl) titanate, and tetramethyl titanate. Orthoesters, Titanium Acetylacetonate, Titanium Tetraacetylacetonate, Polytitanium Acetylacetonate, Titanium Octylene Glycolate, Titanium Lactate, Titanium Triethanolaminate, Titanium Ethylacetacetate, Titanium Diisopropoxybis (Ethylacetacetate) ) Etc. can be mentioned.

The thickness of the anchor layer is preferably 10 to 200 nm, more preferably 20 to 150 nm, and particularly preferably 30 to 100 nm.

[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. For the transfer layer, 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 is applied onto the release layer of the release film, and if necessary, dried. Formed by curing.

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

The active energy ray-curable composition is a composition that is cured by irradiating with active energy rays. Examples of the active energy ray include ultraviolet rays, visible rays, infrared rays, electron beams, α rays, β rays, and γ rays. Of these, ultraviolet rays and electron beams are preferable, and ultraviolet rays are particularly preferably used.

When the transfer layer is composed of a thermosetting composition or an active energy ray-curable composition, the curing time of the transfer layer is not particularly limited, and the type of compound contained in the transfer layer, the type and use of the transfer layer, and the subject. It is appropriately selected depending on the type and application of the body.

Specifically, the curing time of the transfer layer can be carried out by any one 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 the transfer. Further, it can be divided and cured in two or more steps. The 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 the epoxy compound and the compound having an ethylenically unsaturated group in the molecule in the transfer layer is preferably 5% by mass or more with respect to 100% by mass of the total solid content of the transfer layer. 10% by mass or more is more preferable, and 20% by mass or more is particularly preferable. The upper limit is 100% by mass. The above content means the total content when the transfer layer contains two or more kinds of compounds.

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

Preferred examples of the transfer layer containing an epoxy compound include an adhesive layer, a sealing resin layer of a circuit board, and an interlayer insulating resin layer of a multilayer printed wiring board. 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 antireflection 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 antireflection 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 for a circuit board or an interlayer insulating resin for a multilayer printed wiring board, an epoxy compound (epoxy resin) used for a thermosetting adhesive, or the like can be used.

Specific examples of epoxy compounds (epoxy resins) include bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac epoxy resin, cresol novolac type epoxy resin, bisphenol S type epoxy resin, alkylphenol novolac type epoxy resin, and biphenol type epoxy resin. , Naphthalene type epoxy resin, dicyclopentadiene type epoxy resin, epoxidized product of condensate of phenol and aromatic aldehyde having phenolic hydroxyl group, triglycidyl isocyanurate, alicyclic epoxy resin, glycidyl ester type epoxy resin, glycidyl amine Type epoxy resin, hidden in type epoxy resin, isocyanurate type epoxy resin, acrylic acid modified epoxy resin (epoxy acrylate), naphthalene type epoxy resin, linear aliphatic epoxy resin, heterocyclic epoxy resin, spiro ring-containing epoxy resin, halogen Examples include chemicalized epoxy resin.

Specific examples of such epoxy resins include HP4032, HP4032D, HP4700, N-690, N-695 manufactured by Dainippon Ink and Chemicals Co., Ltd., and "Epicoat (registered trademark) manufactured by Japan Epoxy Resin Co., Ltd." ) "807, Epicoat 828EL, Epicoat 152, Nippon Kayaku Co., Ltd.'s" EPPN (registered trademark) "-502H, NC7000L, NC3000H, Toto Kasei Co., Ltd.'s ESN185, ESN475 and the like.

[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 a compound, a (meth) acrylate compound is generally known.

Hereinafter, compounds having an ethylenically unsaturated group in the molecule will be exemplified, but the compound is not limited to these compounds. In the following description, "... (meth) acrylate" is a general term for "... acrylate" and "... methacrylate".

Examples of the compound 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. , Tetrahydrofurfuryl (meth) acrylate, isobornyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxy-3-phenoxy (meth) acrylate and other monofunctional ( 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,
Trimethylol Propanetri (meth) Acrylate, Ditrimethylol Propanetri (Meta) Acrylate, Ditrimethylol Propanetetra (Meta) Acrylate, Glycerin Propoxytri (Meta) Acrylate, Pentaerythritol Tri (Meta) Acrylate, Pentaerythritol Tetra (Meta) 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.

In addition, examples of the compound having an ethylenically unsaturated group in the molecule include a compound having an ethylenically unsaturated group and a urethane bond in the molecule. For example, ethylene glycol, adipic acid, tolylene diisocyanate, 2-hydroxyethyl (meth) acrylate, polyethylene glycol, tolylene diisocyanate, 2-hydroxyethyl (meth) acrylate, hydroxyethylphthalyl (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 Examples thereof include pre-oligomers, pentaerythritol tri (meth) acrylate toluene diisocyanate urethane oligomers, and pentaerythritol tri (meth) acrylate isophorone diisocyanate urethane oligomers.

Examples of the compound having an ethylenically unsaturated group and a urethane bond in the molecule include urethane (meth) acrylate having a polyether skeleton, urethane (meth) acrylate having a polycaprolactone skeleton, and urethane (meth) acrylate having a polycarbonate skeleton.

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

(1a); Compound obtained by reacting polyalkylene glycol (meth) acrylate with an isocyanate compound (1b); Reaction of polyalkylene glycol and an isocyanate compound at a ratio such that the isocyanate group is excessive with respect to the hydroxyl group. Compound obtained by further reacting the compound obtained by reacting with a (meth) acrylate compound having a hydroxyl group Examples of the polyalkylene glycol (meth) acrylate compound used in the synthesis of (1a) above include polyethylene glycol ( Examples thereof include meta) acrylate, polypropylene glycol (meth) acrylate, and polybutylene glycol (meth) acrylate.

As the isocyanate compound used in the synthesis of (1a) above, a polyisocyanate compound containing two or more isocyanate groups in the molecule is preferable, and for example, tolylene diisocyanate, naphthalene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, xylylene diisocyanate, etc. Tris of tetramethylene diisocyanate, hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, methyl-2,6-diisocyanate hexanoate, norbonan diisocyanate, methylenebis-4-cyclohexylisocyanate, tolylene diisocyanate (Methylolpropane adduct, hexamethylene diisocyanate trimerol propane adduct, isophorone diisocyanate trimethylolpropane adduct, tolylene diisocyanate isocyanurate, hexamethylene diisocyanate isocyanurate, hexamethylene isocyanate burette, etc. Poly) isocyanate, block body of the above-mentioned isocyanate, and the like can be mentioned.

Examples of the polyalkylene glycol used in the synthesis of the above (1b) include polyethylene glycol, polypropylene glycol, polybutylene glycol and the like.

As the isocyanate compound used for the synthesis of the above (1b), the same compound as the isocyanate compound used for the synthesis of the above (1a) can be used.

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

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

(2a); Compound obtained by reacting polycaprolactone-modified alkyl (meth) acrylate with an isocyanate compound (2b); Compound obtained by reacting polycaprolactone-modified hydroxyalkyl (meth) acrylate with an isocyanate compound (2c) ); Compound obtained by reacting a long-chain alkyl alcohol, polycaprolactone-modified hydroxyethyl (meth) acrylate and an isocyanate compound Here, the isocyanate compound is the same compound as the isocyanate compound used in the synthesis of (1a) described above. 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 a transesterification reaction of an alkylene glycol and a carbonic acid ester, a reaction of a phosgene or chloralilate ester with an alkylene glycol, or the like.

Examples of the alkylene glycol include ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,9-nonanediol, 1,10-decanediol, and 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 Examples include propane and pentaerythritol.

Examples of the carbonic acid ester 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 and isobutyl. Examples thereof include carbonate, diisobutyl carbonate, cyclocarbonate, diphenyl carbonate, methyldiphenyl carbonate, ethylene carbonate, 1,2-propylene carbonate, 1,2-butylene carbonate and the like.

In addition, examples of the compound having an ethylenically unsaturated group in the molecule include a compound having an ethylenically unsaturated group and a fluorine atom in the molecule. Examples of such compounds include trifluoroethyl (meth) acrylate, tetrafluoropropyl (meth) acrylate, pentafluoropropyl (meth) acrylate, hexafluoropropyl (meth) acrylate, octafluoropentyl (meth) acrylate, and perfluorobutyl. Ethyl (meth) acrylate, perfluorobutyl hydroxypropyl (meth) acrylate, perfluorohexyl ethyl (meth) acrylate, perfluorohexyl hydroxypropyl (meth) acrylate, perfluorooctyl ethyl (meth) acrylate, perfluorooctyl hydroxypropyl ( Meta) acrylate, perfluorodecylethyl (meth) acrylate, heptadecafluorodecyl (meth) acrylate, divinyldodecafluorohexane, 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 ( Meta) acrylate, 2- (perfluorodecyl) ethyl (meth) acrylate, β- (perfluorooctyl) ethyl (meth) acrylate, di- (α-fluoroacrylic acid) -2,2,2-trifluoroethylethylene Glycol, di- (α-fluoroacrylic acid) -2,2,3,3,3-pentafluoropropylethylene glycol, di- (α-fluoroacrylic acid) -2,2,3,3,4,4 4-Hexafluorobutylethylene glycol, di- (α-fluoroacrylic acid) -2,2,3,3,4,5,5,5-nonafluoropentylethylene glycol, di- (α-fluoroacrylic acid) ) -2,2,3,3,4,5,5,6,6-Undecafluorohexylethylene glycol, di- (α-fluoroacrylic acid) -2,2,3,3,4 , 4,5,5,6,6,7,7,7-Tridecafluoroheptylethylene glycol, di- (α-fluoroacrylic acid) -2,2,3,3,4,5,5 6,6,7,7,8,8,8-Pentadecafluorooctylethylene glycol, di- (α-fluoroacrylic acid) -3,3,4,4,5,5,6,6,7,7 , 8,8,8-Trideca Fluorooctyl Acrylate Ethylene glycol, di- (α-fluoroacrylic acid) -2,2,3,3,4,5,5,6,6,7,7,8,8,9,9,9-heptadecafluoro Nonyl ethylene glycol and the like can be mentioned.

Further, as a compound having an ethylenically unsaturated group in the molecule, a polysiloxane compound having an ethylenically unsaturated group can be 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.

Examples of the polysiloxane compound having an ethylenically unsaturated group include the compounds of Production Examples 1-1 to 1-3 of JP-A-2009-84327, or Silaplane FM-0711 and FM-0721 manufactured by Chisso Corporation. , FM-0725, X-24-8201 manufactured by Shin-Etsu Chemical Co., Ltd., 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, BY16-152 manufactured by Toray Dow Corning Co., Ltd. , BY16-152C, BYK-UV3570 manufactured by Big Chemie Japan Co., Ltd., and other commercially available products 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 thermosetting / active energy ray-curable composition containing a thermosetting component and an active energy ray-curable component. Is preferable. As the epoxy compound, the above-mentioned epoxy resin is preferably used. Of these, an adhesive layer (thermosetting adhesive layer) made of a cured product of a thermosetting composition containing an epoxy compound is preferable.

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

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

The adhesive layer can contain the above-mentioned epoxy compound and a thermosetting resin other than the epoxy compound. Examples of other thermosetting resins include novolak-type phenol resins, vinyl phenol resins, and brominated vinyl phenols that crosslink with epoxy resins.

The adhesive layer preferably further contains a curing agent. Examples of the curing agent include amine-based curing agents, guanidine-based curing agents, imidazole-based curing agents, phenol-based curing agents, acid anhydride-based curing agents, hydrazide-based curing agents, carboxylic acid-based curing agents, thiol-based curing agents, or Examples thereof include these epoxy adducts and microencapsulated ones. Further, a curing accelerator such as triphenylphosphine, phosphonium borate, 3- (3,4-dichlorophenyl) -1,1-dimethylurea may be used in combination.

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 a triazine structure-containing novolak resin, a phenol resin, and a melamine resin.

The adhesive layer can contain a thermoplastic resin. Examples of the thermoplastic resin include acrylonitrile-butadiene copolymer (NBR), carboxylated acrylonitrile-butadiene copolymer (carboxylated NBR), acrylonitrile-butadiene-styrene copolymer (ABS), polybutadiene, and styrene-butadiene-ethylene. Examples thereof include polymer (SEBS), (meth) acrylic acid ester resin (acrylic rubber), carboxylated ethylene acrylic rubber, polyvinyl butyral, polyamide, polyester, polyimide, polyamideimide, and polyurethane.

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

The adhesive layer is preferably heat-cured during or after the transfer step. 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. The heating temperature is generally 100 to 200 ° C, preferably 120 to 180 ° C.

When the adhesive layer is an adhesive layer made of a cured product of an active energy ray-curable composition, it shall contain the above-mentioned epoxy compound, a compound having an ethylenically unsaturated group in the molecule, and a photopolymerization initiator. Is preferable. Further, the above-mentioned thermoplastic resin, inorganic or organic filler can be contained. The adhesive layer is preferably cured by irradiating it with active energy rays during or after the transfer.

When the adhesive layer is an adhesive layer made of 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, and light. It preferably contains a polymerization initiator. Further, the above-mentioned thermoplastic resin, inorganic or organic filler can be contained. The adhesive layer is preferably cured by irradiating with heating and / or active energy rays after the transfer step or transfer.

Here, as the compound having an ethylenically unsaturated group in the molecule, the same compound as described above can be used. Further, as the photopolymerization initiator, a compound similar to the compound used for the hard coat layer described later can be used.

The thickness of the adhesive layer is preferably 10 to 200 μm, preferably 20 to 100 μm.

[Hard coat layer]
The transfer layer in the present invention is preferably a hard coat layer. The hard coat layer is applied to prevent the adherend such as the plastic resin molded product described above from being scratched or to impart designability.

From the viewpoint of exerting a scratch-suppressing effect on the adherend to which the hard coat layer is transferred, the pencil hardness of the hard coat layer (specified in JIS K5600-5-4 (1999)) is preferably F or higher, and H. 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 curing 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. Is preferably contained. It is more preferable that the composition is used in combination with the above-mentioned 3-6-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 a photopolymerization initiator include, for example, acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone, benzophenone, 2-chlorobenzophenone, 4,4'-dichlorobenzophenone, and the like. 4,4'-Bisdiethylaminobenzophenone, Michler ketone, benzyl, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, methylbenzoylformate, p-isopropyl-α-hydroxyisobutylphenone, α-hydroxyisobutylphenone, 2, Use carbonyl compounds such as 2-dimethoxy-2-phenylacetophenone and 1-hydroxycyclohexylphenylketone, and sulfur compounds such as tetramethylthium monosulfide, tetramethylthium disulfide, thioxanthone, 2-chlorothioxanthone, and 2-methylthioxanthone. Can be done. These photopolymerization initiators may be used alone or in combination of two or more.

In addition, photopolymerization initiators 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 OX01 manufactured by Ciba Specialty Chemicals Co., Ltd. , DAROCUR TPO, DAROCUR1173, etc., SpeedcureMBB, SpeedcurePBZ, SpeedcureITX, SpeedcureCTX, SpeedcureCTX, SpeedcureEDB, SpeedcureEDB, EsacureONE KAYACURE BMS, KAYACURE DMBI and the like can be mentioned.

When imparting antifouling property (fingerprint resistance) to the hard coat layer, 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 contained. It is preferable to let it.

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

The thickness of the hard coat layer is preferably 0.5 to 20 μm, preferably 1 to 15 μm, and more preferably 2 to 10 μm.

The hard coat layer can be formed by applying an active energy ray-curable composition on the release layer of a release film, drying it if necessary, and then irradiating it with active energy rays. Examples of the active energy include ultraviolet rays, visible rays, infrared rays, electron beams, α rays, β rays, and γ rays. Of these, ultraviolet rays and electron beams are preferable, and ultraviolet rays are particularly preferably used.

The light source for irradiating ultraviolet rays is not particularly limited, and for example, an ultraviolet fluorescent lamp, a low-pressure mercury lamp, a medium-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a carbon arc lamp, a metal halide lamp, a xenon lamp, or the like can be used. .. Further, an ArF excimer laser, a KrF excimer laser, an excimer lamp, a synchrotron radiant light, or the like can also be used. Of these, ultra-high pressure mercury lamps, high pressure mercury lamps, low pressure mercury lamps, carbon arcs, xenon arcs, and metal halide lamps are preferably used. Further, when irradiating ultraviolet rays, it is preferable to irradiate in an atmosphere with a low oxygen concentration, for example, in an atmosphere with an oxygen concentration of 500 ppm or less, because it can be cured 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, and more preferably 1000 mJ / cm ^{2 or less.}

Examples of the method for applying the active energy ray-curable composition include a reverse coating method, a spray coating method, a bar coating method, a gravure coating method, a rod coating method, a die coating method, a spin coating method, and an extrusion coating method. 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 cured in two steps. Examples of the split curing include a method in which the hard coat layer is semi-cured in a laminating step and then completely cured by irradiating an active energy ray after the transfer step or transfer of the hard coat layer.

[Anti-fouling layer]
The transfer layer in the present invention is preferably an antifouling layer. The antifouling layer is a layer having a function of suppressing the adhesion of stain components such as fingerprints or a function of wiping off even if stain components such as fingerprints are attached. Such a function can be represented by, for example, the water contact angle on 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 property 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 preferable. That is, the antifouling layer can be formed by applying the active energy ray-curable composition on the release layer of the release film, drying it if necessary, and then irradiating it with active energy rays to cure it. .. As the irradiation conditions for the active energy rays, the same conditions as those for the hard coat layer described above can be adopted.

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

The thickness of the antifouling layer is preferably 0.01 to 10 μm, more preferably 0.02 to 5 μm, and particularly preferably 0.03 to 3 μm.

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

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

The antireflection layer is preferably composed of a compound having an ethylenically unsaturated group in the molecule and a cured product of an active energy ray-curable composition containing a fluorine compound and / or hollow silica. That is, the antireflection layer can be formed by applying the active energy ray-curable composition on the release layer of the release film, drying it if necessary, and then irradiating it with active energy rays to cure it. .. As the irradiation conditions for the active energy rays, the same conditions as those for the hard coat layer described above can be adopted.

As the fluorine compound, the above-mentioned compound having an ethylenically unsaturated group and a fluorine atom in the molecule is preferably used. In this case, a "compound having an ethylenically unsaturated group in the molecule" other than the above-mentioned fluorine compound is not always necessary, but from the viewpoint of increasing the hardness of the antireflection layer, the above-mentioned 2-6 functional (meth) It preferably contains an acrylate.

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

Particularly preferred embodiments of the antireflection layer include hollow silica and an embodiment containing 2 to 6 functional (meth) acrylates as a compound having an ethylenically unsaturated group in the molecule.

The thickness of the antireflection layer is preferably 0.08 to 0.12 μm, 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. be.

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 a "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 an embodiment 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 a plurality of 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 antireflection layer, the second transfer layer is an adhesive layer for adhering the first transfer layer to the adherend and adheres to the first transfer layer. Examples thereof include an adhesion strengthening layer for improving the adhesion of the layer.

As the adhesive layer, for example, a resin-based adhesive or a hot-melt type adhesive can be used. Examples of the adhesive include acrylic acid ester-based, polyester-based, synthetic rubber-based, epoxy-based, polyurethane-based, ethylene-vinyl acetate-based, polyamide-based, polyvinyl chloride, halogenated polyolefin, nitrocellulose, and copolymers thereof. And so on. Examples of the hot melt type adhesive include polyurethane, polyamide, and polyvinyl chloride.

As the material constituting the adhesion strengthening layer, thermosetting resins such as acrylic urethane resin, salt and vinegar resin, polyester resin, melamine resin and epoxy resin are preferably mentioned.

Further, as the second transfer layer when the first transfer layer is an antifouling layer, a hard coat layer can be mentioned. The hard coat layer is preferably arranged between the antifouling layer and the above-mentioned adhesive layer or adhesion strengthening layer. As the hard coat layer, the same structure as the hard coat layer constituting the first transfer layer described above can be adopted.

Further, examples of the second transfer layer when the first transfer layer is an antireflection layer include a hard coat layer, a high refractive index layer, and a high refractive index hard coat layer. These layers are preferably arranged between the antireflection layer and the above-mentioned adhesive layer or adhesion strengthening layer.

As the hard coat layer, the same structure as 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 metal oxide fine particles having a high refractive index and the above-mentioned compound having an ethylenically unsaturated group in the molecule. Is preferable. Examples of the 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).

The thickness of the high refractive index layer is preferably 0.08 to 0.20 μm, more preferably 0.09 to 0.17 μm. The thickness of the high refractive index hard coat layer is preferably 0.5 to 5.0 μm, more preferably 0.7 to 3.0 μm.

Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited to these Examples.

[Measurement method and evaluation method]
(1) Measurement of surface free energy of release layer Water, diiodomethane, and 1-bromonaphthalene are used as three kinds of liquids whose surface free energy and the values of each component (dispersion force, polarity force, and hydrogen bonding force) are known. The contact angle of each liquid on the release layer was measured with a contact angle meter DropMasterDM501 (manufactured by Kyowa Interface Science Co., Ltd.) at 23 ° C. and 65% RH. The measurement was performed 5 times on one measurement surface, and the average value was taken as the contact angle (θ). Introduced from the Kitazaki-Hata formula from the values of this contact angle (θ) and the known values of each liquid (Method IV by Panzer (described in Vol. 15, No. 3, page 96 of the Journal of the Japan Adhesive Association)). The value of each component was calculated using the following formula.

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

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

E = γSd + γSp + γSh
(2) Measurement of surface roughness SRa The surface roughness SRa of the base film and the release layer is an optical interference type microscope (VertScan2.0, manufactured by Ryoka System Co., Ltd., model: R5300 GL-Lite-AC). The surface morphology was observed and determined in an observation mode = Wave mode, a surface correction = 4th order, a filter = 530 nm White, an objective lens = 50 times, and a measurement area = 252.69 × 189.53 μm. The measurement was performed 5 times per sample, and it was calculated from the average value. The surface roughness SRa of the base film is the surface roughness SRa of the surface to which the release layer is applied.

(3) Measurement of Pencil Hardness of Hard Coat Layer The pencil hardness of the hard coat layer when the transfer layer was a hard coat layer was measured as follows.

After transferring the hard coat layer to the adherend according to the transfer step (8) below, the pencil hardness on the surface of the hard coat layer is manufactured by Shinto Kagaku Co., Ltd. in accordance with JIS K5600-5-4 (1999). It was measured using a 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 When the transfer layer is an antifouling layer, the water contact angle of the antifouling layer was measured as follows.

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

(5) Measurement of Refractive Index of Antireflection Layer and High Refractive Index Hard Coat Layer A coating film (dried) formed by applying a composition for forming the antireflection layer and the high refractive index hard coat layer onto a silicon wafer. For a thickness of about 2 μm), the refractive index of 589 nm was measured with a phase difference measuring device (manufactured by Nikon Corporation: NPDM-1000) under a temperature condition of 25 ° C.

(6) Measurement of the visual reflectance of the antireflection layer The visual reflectance of the antireflection layer when the transfer layer is an antireflection layer was measured as follows.

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

<Measurement of visual reflectance>
Using a spectrophotometer (UV3150PC, manufactured by Shimadzu Corporation), the reflectance (single-sided reflection) was calculated in the wavelength range of 380 to 780 nm at an incident angle of 5 degrees from the measurement surface, and the visual reflectance (in JIS Z8701-1999). The specified reflex stimulation value Y) was determined. The spectral solid angle is measured with a spectrophotometer, and the reflectance (single-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 (However, 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 the XYZ display system R (λ): Spectral solid angle reflectance.

(7) Evaluation of Applyability of Transfer Layer Each composition of the transfer layer was applied onto the release layer of the release film in the manner of the following Examples, and the coatability was evaluated according to the following criteria.
A (Good); When a uniform coating film with a good appearance is obtained B (Yes); When a slight coating unevenness is confirmed on the coating film but the appearance is within the standard C (No); Strong repellent on the coating film Or when strong coating unevenness is confirmed and the appearance is out of specification.

(8) Evaluation of release property of release film of transfer film In a step of transferring a transfer layer of a transfer film in which an adhesive layer, a hard coat layer, an antifouling layer or an antireflection layer is laminated as a transfer layer to an adherend. The peelability between the release film and the transfer layer was evaluated as follows. The adherend was changed as follows according to the type of transfer layer.

<Subject>
-When the transfer layer is an adhesive layer; a substrate in which a polyimide layer having a thickness of 25 μm is laminated on a rough surface of a rolled copper foil (manufactured by JX Nippon Mining & Metals Co., Ltd., thickness 35 μm). The transfer surface of the adhesive layer is the surface of the rolled copper foil.
-The transfer layer is a hard coat layer, an antifouling layer or an antireflection layer; a polyethylene terephthalate film having a thickness of 188 μm (“Lumilar®” U48 manufactured by Toray Industries, Inc.)
<Transfer process>
A test laminate was prepared by superimposing the transfer layer surface of the transfer film and the adherend. This laminate was inserted into a heating press device (2ton vacuum heater press model number MKP-150TV-WH manufactured by Mikado Technos Co., Ltd.) and heat-pressed at a press temperature of 160 ° C. and a press pressure of 2 MPa for 20 minutes. Then, the laminated body was taken out, left at room temperature for 1 hour, and then the release film was peeled off from the laminated body, and the peelability was evaluated according to the following criteria.

<Evaluation of peelability>
A (good); when peeling can be done easily and smoothly B (possible); when peeling can be done with a little force C (impossible); when peeling cannot be done without applying considerable force [1st transfer layer]
The composition for obtaining an adhesive layer containing an epoxy compound, a hard coat layer, an antifouling layer and an antireflection layer containing a compound having an ethylenically unsaturated group in the molecule is shown below.

<Composition 1 for adhesive layer>
As an epoxy compound, 40 parts by mass of bisphenol A type epoxy resin ("Epicron 840-S" manufactured by Dainippon Ink and Chemicals Co., Ltd.), 40 parts by mass of novolac type phenol resin ("PR-53647" manufactured by Sumitomo Bakelite Co., Ltd.), 20 parts by mass of phenoxy resin ("YL-6954" manufactured by Japan Epoxy Resin Co., Ltd.), 5 parts by mass of silica (manufactured by Nippon Aerodil Co., Ltd.) with an average particle diameter of 16 nm, octylriethoxysilane (Shinetsu Chemical Co., Ltd.) as a silane coupling agent (Manufactured by Kogyo Co., Ltd.) 0.5 parts by mass, 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 an epoxy compound, 45 parts by mass of a polyfunctional solid epoxy containing a triphenol methane skeleton (trade name "EP1032H60" manufactured by Japan Epoxy Resin Co., Ltd.) and a bisphenol F type liquid epoxy (trade name "YL983U" manufactured by Japan Epoxy Resin Co., Ltd.) ) 15 parts by mass, 5 parts by mass of flexible epoxy resin (trade name "YL7175" manufactured by Japan Epoxy Resin Co., Ltd.), 2,4-diamino-6- [2'-methylimidazolyl- (1') as a curing agent ] -Ethyl-s-triazine isocyanuric acid adduct (trade name "2MAOK-PW" manufactured by Shikoku Kasei Co., Ltd.) 4 parts by mass, 2-methylglutaric acid 4 parts by mass, silica with an average particle diameter of 100 nm (Co., Ltd.) Admatex product name "SE1050") 10 parts by mass, methacrylic surface-treated nanosilica with an average particle diameter of 50 nm (Admatex product name "YA050C-SM") 55 parts by mass, organic resin particles (Rome and Hearth) Japan Co., Ltd. trade name "EXL-2655": core shell type organic fine particles) 10 parts by mass, glycidylsilane coupling agent (Toray Dow Corning Co., Ltd. trade name "SH6040") 2 parts by mass, and methyl ethyl ketone The mixture was charged to a solid concentration of 60% by mass and stirred with a bead mill for 30 minutes. After that, 20 parts by mass of phenoxy resin (trade name "ZX-1356-2" manufactured by Toto Kasei Co., Ltd.) was added, and the bead mill was used again. Prepared by stirring for 30 minutes.

<Composition 3 for adhesive layer>
100 parts by mass of epoxy compound (manufactured by Japan Epoxy Resin Co., Ltd., trade name "Epicoat 828EL"), 40 carboxylated NBR (manufactured by Nippon Zeon Co., Ltd., trade name "Nipol (registered trademark)" 1072 ") By mass, 25 parts by mass of 4,4'-diaminodiphenyl sulfone as a curing agent was dissolved and dispersed in methyl ethyl ketone to prepare a solid content concentration of 30% by mass.

<Composition 1 for hard coat layer>
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, 58 parts by mass, an ethylenically unsaturated group and a urethane bond in the molecule 37 parts by mass of urethane acrylate oligomer (trade name "UN-901T" manufactured by Negami Kogyo Co., Ltd.), photopolymerization initiator ("Irgacure (registered trademark)" 184 manufactured by Ciba Specialty Chemicals Co., Ltd.) 5 parts by mass was dissolved in methylisobutylketone to prepare a coating solution having a solid content concentration of 20% by mass.

<Composition for hard coat layer 2>
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, and not ethylenically in the molecule synthesized below. 140 parts by mass of compound (UA) having a saturated group and urethane bond, 5 parts by mass of photopolymerization initiator ("Irgacure (registered trademark)" 907 manufactured by Ciba Specialty Chemicals Co., Ltd.), solid content of the following reactive silica 5% by mass was mixed by mass ratio (ratio of the composition to the total solid content) and diluted with methyl ethyl ketone to prepare a solid content concentration of 20% by mass.

<Synthesis of compound (UA)>
3. In a four-necked flask, add 3180 parts by mass of bisphenol F-type diepoxy resin (also manufactured by Toto Kasei Co., Ltd., trade name "Epototo YDF-8170C"), 1440 parts by mass of acrylic acid, and hydroquinone monomethyl ether as a polymerization inhibitor. 6 parts by mass, 23 parts by mass of dimethylaminoethyl methacrylate (trade name "Acrylic acid DM" manufactured by Mitsubishi Rayon Co., Ltd.) was added as a synthetic catalyst, the temperature was raised to 95 ° C. with stirring, and the temperature was maintained at 95 ° C. The reaction was continued for 14 hours. When the acid value became 1 mgKOH / g or less, the mixture was cooled to an internal temperature of 60 ° C. to obtain an epoxy (meth) acrylate compound.

Next, 298 parts by mass of the epoxy (meth) acrylate compound and 711.3 parts by mass of ethyl acetate were placed in a four-necked flask and heated to an internal temperature of 60 ° C. 0.21 parts by mass of di-n-butyltin dilaurate was added as a synthesis catalyst, and 199 parts by mass of methylcyclohexylene diisocyanate (trade name "Takenate 600" manufactured by Mitsui Chemicals Polyurethane Co., Ltd.) was added for 1 hour while stirring. Dropped over. The reaction was continued for 2 hours after the completion of the dropping, 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) and pentaerythritol tetraacrylate (Toa Synthetic Co., Ltd.). ), The trade name "Aronix M-306") 187 parts by mass of the mixture was added dropwise over 1 hour. The reaction was continued for 5 hours after the dropping to obtain a urethane (meth) acrylate compound having a mass average molecular weight of 19,800.

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

<Composition for hard coat layer 3>
An ultraviolet curable resin coating solution (“UV-7550B” manufactured by Nippon Synthetic Chemical Co., Ltd.) containing a compound having an ethylenically unsaturated group and a urethane bond in the molecule is mixed with methyl ethyl ketone to have a solid content concentration of 20% by mass. Diluted as.

<Composition for hard coat layer 4>
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 the molecule was prepared with methyl ethyl ketone to have a solid content concentration of 30% by mass. ..

<Composition for antifouling layer 4>
Ultraviolet curable hard coat paint containing a compound having an ethylenically unsaturated group and a fluorine atom in the molecule (trade name "Forseed No. 421C" of China Paint Co., Ltd.) with methyl ethyl ketone to a solid content concentration of 30% by mass Prepared.

<Composition for antireflection layer 1>
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, 57 parts by mass, isopropyl alcohol dispersion of hollow silica particles (JGC Catalyst) Kasei Co., Ltd .: Solid content concentration 20% by mass, average particle size 60 nm) in 40 parts by mass in terms of solid content, and photopolymerization initiator (Ciba Specialty Chemicals Co., Ltd. "Irgacure (registered trademark)" 184 ) Prepared by dispersing or dissolving 3 parts by mass in methyl ethyl ketone. The refractive index of this composition was 1.37.

[Second transfer layer]
<Composition for adhesive layer>
A hot melt type adhesive (“Aron Melt (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 Negami 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 the base film constituting the release film.

<Polyester film 1>
A polyester film of Toray Industries, Inc. (“Lumirer (registered trademark)” R75X) was prepared. This polyester film had a thickness of 25 μm and a surface roughness SRa of 25 nm.

<Polyester film 2>
A polyester film of Toray Industries, Inc. (“Lumirer (registered trademark)” S10) was prepared. This polyester film had a thickness of 100 μm and a surface roughness SRa of 25 nm.

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

[Example 1]
A release film was prepared in the following manner.

The following composition for an anchor layer is applied to one surface of the polyester film 1 with a gravure coater, dried and heated at 120 ° C., and then the following composition for a release layer p1 is applied with a gravure coater to 100 ° C. After pre-drying, the anchor layer and the release layer were laminated by heating and drying at 160 ° C. 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>
3-glycidoxypropyltrimethoxysilane (trade name "BY24-846B" manufactured by Toray Dow Corning Co., Ltd .; content 98% by mass) 5 parts by mass, 3-methacryloxypropyltrimethoxysilane (Tole Dow Corning) Trade name "XIAMETER" OFS-6030 SILANE manufactured by Co., Ltd., content 99% by mass) 1 part by mass, bis (ethylacetoacetate) (2,4-pentanionate) aluminum (Toray Dow Corning (Toray Dow Corning) as aluminum chelate It was prepared by adding and mixing 2 parts by mass of trade name "BY24-846E" manufactured by Co., Ltd .; content 38% by mass) to a mixed solvent of 50 parts by mass of toluene and 50 parts by mass of isopropyl alcohol.

<Composition for release layer p1>
-Silicone-modified alkyd resin; 100 parts by mass of the trade name "X-62-9022" (silicone modification rate is 1% by mass, containing a melamine cross-linking agent) manufactured by Shin-Etsu Chemical Industry Co., Ltd.-Acid catalyst; p-toluenesulfonic acid (Product name "CAT-PC-80" manufactured by Shin-Etsu Chemical Industry Co., Ltd.) is 1.3 parts by mass and solvent; 245 parts by mass of toluene and 165 parts by mass of methyl ethyl ketone [Example 2]
A release film was prepared in the same manner as in Example 1 except that the composition for the 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 of the trade name "KS-881" (silicone modification rate is 5% by mass, containing a melamine cross-linking agent) manufactured by Shin-Etsu Chemical Industry Co., Ltd.-Acid catalyst; p-toluenesulfonic acid (Shin-Etsu) 1.3 parts by mass / solvent of trade name "CAT-PC-80" manufactured by Chemical Industry Co., Ltd .; 240 parts by mass of toluene and 160 parts by mass of methyl ethyl ketone [Example 3]
A release film was prepared in the same manner as in Example 1 except that the composition for the 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 the trade name "KS-883" (silicone modification rate: 10% by mass, containing melamine cross-linking agent) manufactured by Shin-Etsu Chemical Industry Co., Ltd.-Acid catalyst; p-toluenesulfonic acid (Shin-Etsu) 1.3 parts by mass / solvent of trade name "CAT-PC-80" manufactured by Chemical Industry Co., Ltd .; 240 parts by mass of toluene and 160 parts by mass of methyl ethyl ketone [Example 4]
A release film was prepared in the same manner as in Example 1 except that the composition for the 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 of the trade name "KS-882" (silicone modification rate: 20% by mass, containing melamine cross-linking agent) manufactured by Shin-Etsu Chemical Industry Co., Ltd.-Acid catalyst; p-toluenesulfonic acid (Shin-Etsu) 1.3 parts by mass / solvent of trade name "CAT-PC-80" manufactured by Chemical Industry Co., Ltd .; 240 parts by mass of toluene and 160 parts by mass of methyl ethyl ketone [Example 5]
A release film was prepared in the same manner as in Example 1 except that the composition for the 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 parts by mass of the trade name "Tessfine 309" (silicone-modified alkyd resin / melamine cross-linking agent (mass ratio) = 65/35, silicone modification rate: 3% by mass) manufactured by Hitachi Chemical Co., Ltd. -Acid catalyst: 1.3 parts by mass of p-toluene sulfonic acid (trade name "CAT-PC-80" manufactured by Shin-Etsu Chemical Industry Co., Ltd.) -Solvent: 420 parts by mass of toluene, 280 parts by mass of methyl ethyl ketone [Implementation] Example 6]
In Example 2, a release film was produced in the same manner as in Example 2 except that the polyester film 1 was changed to the polyester film 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]
In Example 2, a release film was produced in the same manner as in Example 2 except that the polyester film 1 was changed to the polyimide film 1. 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 for release layer p6 was applied to one surface of the polyester film 1 with a gravure coater, pre-dried at 100 ° C., and then heat-dried at 160 ° C. to laminate the 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 "LTC750A" 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. It was mixed with 500 parts by mass of toluene and 500 parts by mass of n-heptane.

[Comparative Example 2]
A release film was prepared in the same manner as in Comparative Example 1 except that the composition for the 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 melamine resin (trade name "RP-50" manufactured by Mitsuba Research Institute Co., Ltd.), 4 parts by mass of curing agent ("Plus Coat (registered trademark)" DEP clear manufactured by WASHIN CHEMICAL INDUSTRIES CO., LTD. Was mixed with 50 parts by mass of toluene and 50 parts by mass of cyclohexanone.

<Evaluation>
Table 1 shows the evaluation results of the release film obtained above.

[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>
On the release layer of the release film produced in Examples 1 to 7 and Comparative Examples 1 and 2, the adhesive layer compositions 1 to 3 containing an epoxy compound are dried so that the thickness after drying is 25 μm. It was applied using an applicator and dried at 150 ° C. to form an 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 transfer film is prepared by laminating a hard coat layer as a first transfer layer and an adhesive layer as a second transfer layer in this order on the release layers of the release films prepared in Examples 1 to 7 and Comparative Examples 1 and 2. bottom.

<Lamination of hard coat layer (first transfer layer)>
The compositions 1 to 4 for the hard coat layer are applied using a wire bar so that the thickness after drying and curing is 7 μm, dried at 90 ° C., ^{irradiated with ultraviolet rays at 500 mJ / cm 2} and cured to hard coat. The layers were laminated.

<Lamination of adhesive layer (second transfer layer)>
A hot melt type adhesive layer (“Aron Melt (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]
A transfer film is prepared by laminating an antifouling layer as a first transfer layer and an adhesive layer as a second transfer layer in this order on the release layers of the release films prepared in Examples 1 to 7 and Comparative Examples 1 and 2. bottom.

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

<Lamination of adhesive layer (second transfer layer)>
A hot melt type adhesive (“Aron Melt (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 4.

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

<Lamination of antireflection layer (first transfer layer)>
The antireflection layer composition 1 is applied using a wire bar so that the thickness after drying and curing is 0.1 μm, dried at 90 ° C., ^{irradiated with ultraviolet rays at 300 mJ / cm 2} and cured to prevent reflection. The layers were laminated.

<Lamination of high refractive index hard coat layer (second transfer layer)>
The composition for a high refractive index hard coat layer is applied using a wire bar so that the thickness after drying and curing is 5 μm, dried at 90 ° C., ^{irradiated with ultraviolet rays at 500 mJ / cm 2} and cured to achieve high refractive index. The rate hard coat layer was laminated.

<Lamination of adhesive layer (second transfer layer)>
A hot melt type adhesive (“Aron Melt (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 5.

Claims (10)

A release film used for a transfer film in 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 is a silicone on a base film. A release layer containing a modified alkyd resin is provided , and the content of the silicone-modified alkyd resin in the release layer is 40% by mass or more with respect to 100% by mass of the total solid content of the release layer. A release film for a transfer film having a surface free energy of 22 to 30 mJ / m ^2. A release film used for a transfer film in which a transfer layer containing a compound having an ethylenically unsaturated group in the molecule is laminated, and the release layer containing a silicone-modified alkyd resin is provided on a base film. Also, a release film for transfer film. The release film for a transfer film according to claim 1 or 2 , 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 antireflection layer. The release film for a transfer film according to claim 2 , wherein the content of the silicone-modified alkyd resin in the release layer is 40% by mass or more with respect to 100% by mass of the total solid content of the release layer. The release film for a transfer film according to any one of claims 1 to 4 , wherein the release layer further contains a melamine cross-linking agent. The release film for a transfer film according to any one of claims 1 to 5 , wherein an anchor layer is arranged between the base film and the release layer. The release film for a transfer film according to claim 6 , wherein the anchor layer contains a silane compound and a metal complex having an organic ligand. The release film for a transfer film according to claim 7 , 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. Transfer on the release layer of the release film for transfer film according to any one of claims 1 to 8 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 film in which layers are laminated. The transfer film according to claim 9 , 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 antireflection layer.