JP6195146B2 - Protective layer transfer sheet and method for producing the same - Google Patents

Description

  The present invention relates to a protective layer transfer sheet, and more particularly to a protective layer transfer sheet that has good transferability, excellent surface strength, and can be manufactured at low cost.

  IC cards such as ID cards such as ID cards and cash cards such as banks have personal information such as face photos, addresses and names recorded on the surface, and security processing is applied to prevent the contents from being forged or altered. Has been. For example, IC cards provided with holograms on the surface are widely distributed. A protective layer is provided on the surface of such an IC card using a protective layer transfer sheet in order to protect recorded information and holograms.

  The protective layer transfer sheet has a configuration in which a transferable hard coat layer is provided on a support, and a hard coat layer (protective layer) of the protective layer transfer sheet is provided on the surface of a transfer target such as an IC card. By transferring, hard coat performance can be imparted to the surface of the transfer object. As such a protective layer transfer sheet, generally, an ultraviolet curable resin layer, an intermediate layer subjected to pattern printing or the like on a support such as a PET film via a release layer or a release layer, and an adhesive layer Those having a layer structure in which are stacked in order.

  Since the ultraviolet curable resin layer constituting the protective layer transfer sheet is responsible for protecting the surface of the transfer object, it is required to have high hard coat performance, that is, high surface strength. For example, Japanese Patent Laid-Open No. 2001-1673 (Patent Document 1) proposes to increase the surface strength by increasing the thickness of the photo-curing resin layer. However, when the photo-curing resin layer is thickened, the foil breakage at the time of transfer is deteriorated, and the transferability is lowered. Therefore, in order to improve the surface strength of the photo-curing resin layer while maintaining the transferability, a transfer layer is transferred twice by using a protective layer transfer sheet having a normal transferability and a good thickness. It is conceivable to provide a protective film having a certain thickness on the surface. For example, in Japanese Patent Application Laid-Open No. 2001-138664 (Patent Document 2), using a protective layer transfer sheet provided with a cured layer (photocured resin layer) having a thickness of about 5 to 25 μm, the transfer target is performed twice or more. It has been proposed to transfer a cured layer to the body. Although this method can form a protective layer having excellent surface strength on the surface of the transferred material while maintaining transferability by transferring twice, there is a problem in terms of cost because the number of steps increases.

  By the way, Unexamined-Japanese-Patent No. 2001-138673 (patent document 3) uses the acrylic polymer which has a specific unsaturated group as a hardened layer of a protective layer transfer sheet, and is excellent in surface strength and also in durability. It is proposed that an excellent protective layer transfer sheet can be obtained.

Japanese Patent Laid-Open No. 2001-1673 JP 2001-138664 A JP 2001-138664 A

  When producing the protective layer transfer sheet as described above, a release layer or a release layer is formed on the support, and a coating liquid containing a resin that can be cured by ultraviolet rays or the like is applied to the surface and irradiated with ultraviolet rays. By doing so, the resin is cured to form a protective layer. When the irradiation energy of ultraviolet rays is increased during the formation of the protective layer, the present inventors increase the degree of polymerization and / or crosslinking of the resin and improve the surface strength of the cured resin, but the foil breaks during transfer. The transferability is deteriorated and the transferability is lowered. Conversely, when the irradiation energy of ultraviolet rays is lowered, a protective layer transfer sheet having good transferability can be obtained, but the surface strength of the resin serving as the protection layer may be reduced. I understood. As a result of further studies, the present inventors have now applied UV irradiation to semi-cure the resin in the resin curing step when forming a protective layer using a specific resin composition, and then the second UV irradiation. As a result, it was found that a protective layer transfer sheet having good transferability and excellent surface strength can be obtained. The protective layer of the protective layer transfer sheet obtained by the method as described above has excellent surface strength and can impart sufficient hard coat performance to the surface of the transfer object by only one transfer, so that the protective layer can be provided at a low cost. It is possible to manufacture the transfer target provided.

  Accordingly, an object of the present invention is to provide a protective layer transfer sheet that has good transferability, is excellent in surface strength, and is inexpensive.

  Another object of the present invention is to provide a method for producing the above protective layer transfer sheet.

The protective layer transfer sheet according to the present invention is a protective layer transfer sheet comprising at least a support and an actinic ray curable resin layer provided on the support via a release layer and / or a release layer. And
The actinic ray curable resin layer is obtained by curing an actinic ray curable resin containing an unsaturated group-containing acrylic copolymer by irradiating the actinic ray at least twice or more. It is.

  In the protective layer transfer sheet according to the present invention, it is preferable that the actinic ray curable resin layer contains fine particles.

  In the protective layer transfer sheet according to the present invention, the fine particles preferably have an average particle size of 0.05 to 5 μm.

  In the protective layer transfer sheet according to the present invention, the fine particles are preferably contained in the actinic ray curable resin layer in a proportion of 0.01 to 30% by mass.

（式中、Ｒ_１およびＲ_２は、それぞれ独立して、水素原子またはメチル基を表し、Ｒ_３は、水素原子、アルキル基またはアリール基であるが、Ｒ_２がメチル基である場合にＲ_３は水素原子であり、Ｌは２価の連結基を表す。）
で表されるモノマー単位を含むことが好ましい。 In the protective layer transfer sheet according to the present invention, the unsaturated group-containing acrylic copolymer has the following general formula (1):

(In the formula, R ₁ and R ₂ each independently represent a hydrogen atom or a methyl group, and R ₃ represents a hydrogen atom, an alkyl group, or an aryl group, but when R ₂ is a methyl group, ₃ represents a hydrogen atom, and L represents a divalent linking group.)
It is preferable that the monomer unit represented by these is included.

  Moreover, in the protective layer transfer sheet by this invention, it is preferable that the said unsaturated group containing acrylic copolymer contains 0.01-50 mass% of monomer units of the said General formula (1).

  In the protective layer transfer sheet according to the present invention, the unsaturated group-containing acrylic copolymer preferably has an acid value of 5 to 500 mgKOH / g.

  Moreover, in the protective layer transfer sheet by this invention, it is preferable that the mass mean molecular weights of the said unsaturated group containing acrylic copolymer are 3000-100000.

  In the protective layer transfer sheet according to the present invention, the actinic ray curable resin preferably contains 10 to 80% by mass of the unsaturated group-containing acrylic copolymer.

  Moreover, in the protective layer transfer sheet by this invention, it is preferable that the thickness of the said actinic-light curable resin layer is 5 micrometers-20 micrometers.

  Moreover, it is preferable that the protective layer transfer sheet according to the present invention further includes an adhesive layer provided on the actinic ray curable resin layer.

  The protective layer transfer sheet according to the present invention preferably further comprises an intermediate layer provided between the actinic ray curable resin layer and the adhesive layer.

A method for producing a protective layer transfer sheet according to another aspect of the present invention is a method for producing the protective layer transfer sheet described above,
Forming a release layer and / or a release layer on the support;
On the release layer and / or release layer, a coating solution containing an actinic ray curable resin is applied to form a coating film,
The coating film is irradiated with actinic rays at least twice or more to form an actinic ray curable resin layer.

  Moreover, in the manufacturing method of the protective layer transfer sheet by this invention, it is preferable that irradiation of the said actinic light is performed at least 2 times or more at another process.

  In the method for producing a protective layer transfer sheet according to the present invention, the irradiation with the actinic ray is performed such that the irradiation energy at the second irradiation is higher than the irradiation energy at the first irradiation. Is preferred.

  Moreover, in the manufacturing method of the protective layer transfer sheet by this invention, it is preferable that the actinic ray at the time of the said 1st irradiation is an ultraviolet-ray.

In the method for producing a protective layer transfer sheet according to the present invention, it is preferable to perform the first irradiation with ultraviolet rays having a peak illuminance of 10 to 350 mW / cm ² and an integrated exposure amount of 10 to 200 mj / cm ² .

  Moreover, in the manufacturing method of the protective layer transfer sheet by this invention, it is preferable that the actinic light of the said 2nd irradiation is an ultraviolet-ray or an electron beam.

Moreover, in the manufacturing method of the protective layer transfer sheet by this invention, it is preferable to perform the 2nd irradiation with the ultraviolet-ray of integrated exposure amount 50-500mj / cm < ² >.

  Moreover, in the manufacturing method of the protective layer transfer sheet by this invention, it is preferable to perform 2nd irradiation with the electron beam of 50-300 kGy of irradiation dose.

  In the method for producing a protective layer transfer sheet according to the present invention, the coating film is irradiated with the first actinic ray, and then an intermediate layer is laminated on the coating film, and the intermediate layer is interposed through the intermediate layer. It is preferable to perform the second active light irradiation.

  In the method for producing a protective layer transfer sheet according to the present invention, the coating film is irradiated with an actinic ray for the first time, and then an adhesive layer is laminated on the coating film, and 2 It is preferable to perform the second active light irradiation.

  In the method for producing a protective layer transfer sheet according to the present invention, after the intermediate layer is formed, an adhesive layer is further laminated on the intermediate layer, and the second actinic ray is passed through the intermediate layer and the adhesive layer. It is preferable to perform irradiation.

  In the method for producing a protective layer transfer sheet according to the present invention, it is preferable to perform the second irradiation after elapse of at least 2 hours after the first irradiation.

  According to the present invention, after applying a coating liquid comprising an actinic ray curable resin comprising an unsaturated group-containing acrylic copolymer to form a coating film, the coating film is irradiated with actinic rays at least twice or more. By irradiating to form an actinic ray curable resin layer, it is possible to obtain a protective layer transfer sheet having excellent transferability and excellent surface strength. In addition, the obtained protective layer transfer sheet has excellent surface strength and can impart sufficient hard coat performance to the surface of the transferred material by only one transfer, so a protective layer is formed on the surface of the transferred material at a low cost. can do.

It is a cross-sectional schematic diagram of the protective layer transfer sheet by one Embodiment of this invention. It is the schematic process figure which showed each process by one Embodiment of the manufacturing method of the protective layer transfer sheet of this invention. It is the schematic process drawing which showed each process by other embodiment of the manufacturing method of the protective layer transfer sheet of this invention. It is the schematic process drawing which showed each process by other embodiment of the manufacturing method of the protective layer transfer sheet of this invention.

<Definition>
In this specification, an actinic ray curable resin means a precursor or a composition before irradiation with an actinic ray, and an actinic ray curable resin obtained by irradiating an actinic ray to cure the actinic ray curable resin. Let's say.

  In the present specification, the actinic ray means radiation that chemically acts on the actinic ray curable resin to promote polymerization, and specifically, visible light, ultraviolet ray, X-ray, electron beam. , Α ray, β ray, γ ray and the like.

<Protective layer transfer sheet>
Embodiments of the present invention will be described in detail with reference to the drawings. FIG. 1 is a schematic cross-sectional view of a protective layer transfer sheet according to an embodiment of the present invention. As shown in FIG. 1, a protective layer transfer sheet according to the present invention comprises a support 1 and an actinic ray curable resin layer 4 provided on the support 1 via a release layer and / or a release layer 2. At least. An intermediate layer 5 and an adhesive layer 6 may be provided on the actinic ray curable resin layer 4. When the protective layer 7 is transferred to a transfer target (not shown) using such a protective layer transfer sheet 10, when the actinic ray curable resin layer 4 (the intermediate layer 5 and the adhesive layer 6 are provided) The actinic ray curable resin layer 4, the intermediate layer 5, and the adhesive layer 6) are transferred as a protective layer 7 to the transfer target. Hereinafter, each layer constituting the protective layer transfer sheet according to the present invention will be described.

  The support has heat resistance that can withstand thermal energy (for example, heat of a thermal head) when transferring the protective layer from the protective layer transfer sheet to the transfer target, and has mechanical strength and solvent resistance that can support the protective layer. If it has the property, it can be used without a restriction | limiting in particular. For example, polyester resins such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyethylene terephthalate-isophthalate copolymer, terephthalic acid-cyclohexanedimethanol-ethylene glycol copolymer, polyethylene terephthalate / polyethylene naphthalate coextruded film Polyamide resins such as nylon 6 and nylon 66, polyolefin resins such as polyethylene, polypropylene and polymethylpentene, vinyl resins such as polyvinyl chloride, acrylic resins such as polyacrylate, polymethacrylate and polymethyl methacrylate Imide resins such as polyimide and polyetherimide, polyarylate, polysulfone, polyethersulfone, polyphenylene Engineering resins such as nylene ether, polyphenylene sulfide (PPS), polyaramid, polyether ketone, polyether nitrile, polyether ether ketone, polyether sulfite, and styrenes such as polycarbonate, polystyrene, high impact polystyrene, AS resin, ABS resin Examples thereof include cellulose films such as resins, cellophane, cellulose acetate, and nitrocellulose.

  The support may be a copolymer resin or a mixture (including an alloy) containing the above-mentioned resin as a main component, or a laminate composed of a plurality of layers. The support may be a stretched film or an unstretched film, but it is preferable to use a film stretched in a uniaxial direction or a biaxial direction for the purpose of improving strength. The support is used as a film, sheet or board comprising at least one layer of these resins. Among the supports made of the above-described resins, polyester films such as polyethylene terephthalate and polyethylene naphthalate are preferably used because of their excellent heat resistance and mechanical strength, and among these, a polyethylene terephthalate film is more preferable.

  Moreover, unevenness | corrugation can be provided to the support body surface as needed for blocking prevention. Examples of means for forming irregularities on the support include kneading of a matting agent, sand blasting, hairline processing, mat coating, or chemical etching. In the case of mat coating, either organic or inorganic materials may be used.

  A support having a thickness of 2.5 to 50 μm can be suitably used. If the thickness of the support is too thick, the mechanical strength is high, but the transfer of thermal energy when transferring the protective layer from the protective layer transfer sheet is insufficient, and the transferability tends to be lowered. On the other hand, if the thickness of the support is too thin, the mechanical strength may be insufficient and the protective layer may not be supported.

  As will be described later, the support is provided with a release layer and / or a release layer on the surface thereof. Therefore, a corona discharge treatment, a plasma treatment, an ozone treatment, Easy adhesion treatment such as frame treatment, primer (also called an anchor coat, adhesion promoter, or easy adhesive) coating treatment, pre-heat treatment, dust removal treatment, vapor deposition treatment, alkali treatment, and application of an antistatic layer may be performed. Moreover, you may add additives, such as a filler, a plasticizer, a coloring agent, and an antistatic agent, to a support body as needed.

  The release layer and / or release layer 2 provided on the support 1 is for peeling the protective layer 7 provided on these layers from the protective layer transfer sheet and transferring it to a transfer target (not shown). Of layers. When the protective layer is peeled from the protective layer transfer sheet, the layer that is peeled together with the protective layer is the release layer, only the protective layer is peeled off, and the layer that remains on the support side is the release layer. is there.

The release layer can also be formed using a release agent such as waxes, silicone wax, silicone resin and the like. The release layer is a coating solution prepared by dissolving or dispersing the above-described release agent with an additive or the like in an appropriate solvent, a coating method such as a roll coating method or a spray coating method, or a gravure printing method. It can be formed by applying and drying on a support by a known means such as a screen printing method. The coating liquid is applied so that the thickness of the coating film when dried is about 0.0001 to 5 g / m ² .

  As the release layer, a release resin, a resin containing a release agent, or a curable resin that can be polymerized or cross-linked by irradiation with actinic rays can be suitably used. For example, fluorine resin, silicone, melamine Resins, epoxy resins, polyester resins, acrylic resins, fiber base resins, waxes, melamine resins, and the like can be given. Examples of the resin containing a release agent include a resin obtained by adding or copolymerizing a release agent such as a fluorine-based resin, silicone, and various waxes. Examples of the curable resin that can be polymerized or crosslinked by irradiation with actinic rays include monomers and oligomers having functional groups that are polymerized or cured by irradiation with actinic rays such as ultraviolet rays (UV) and electron beams (EB). Examples thereof include curable resins.

  As the resin to which the release agent is added, an acrylic resin, a vinyl resin, a polyester resin, and a fiber resin may be used. From the viewpoint of heat resistance, a cyclic olefin resin, a norbornene resin, and a polycarbonate resin. Polyarylate resin, polyamideimide resin, polyetherimide resin, polysulfone resin and the like can be preferably used. Among these, a cyclic olefin resin and a norbornene resin are preferable, and a norbornene resin is more preferable. Further, the release layer may be a copolymer resin or a mixture (including an alloy) containing the above resin as a main component. Among the thermoplastic resins described above, those having a glass transition temperature (Tg) of 120 to 200 ° C are preferable.

  Examples of the cyclic olefin-based resin containing a cyclic structure include (a) a norbornene polymer, (b) a monocyclic olefin polymer, (c) a cyclic conjugated diene polymer, and (d) a vinyl alicyclic ring. And a hydride of (a) to (d). Among these, from the viewpoint of excellent heat resistance and mechanical strength, a norbornene polymer hydride, a vinyl alicyclic hydrocarbon polymer, and a hydride thereof are preferable, and a hydride of a norbornene polymer is preferable. More preferred.

  The release layer is formed by applying a coating solution in which the above resin is dispersed or dissolved in a solvent by a known means such as roll coating, reverse roll coating, gravure coating, reverse gravure coating, bar coating, rod coating, etc. You may form by apply | coating and drying on top, and may form a peeling layer on a support body by the extrusion coating method. Furthermore, the coating film may be heat-dried or aged at a temperature of 30 ° C. to 120 ° C. to form a release layer, or the coating film may be irradiated with active light to be polymerized or crosslinked to form a release layer. .

  The thickness of the release layer is usually about 0.0001 μm to 5.0 μm, preferably about 0.0001 μm to 1.0 μm. The thinner the release layer, the better. However, if the thickness is 0.001 μm or more, the film is formed better, and the release force is stable.

  Next, the actinic ray curable resin layer constituting the protective layer transfer sheet according to the present invention will be described. The actinic ray curable resin layer is formed by applying an actinic ray curable resin containing an unsaturated group-containing acrylic copolymer on a release layer and / or a release layer as described later, It is formed by curing with actinic rays.

で表されるモノマー単位を含む。 The unsaturated group-containing acrylic copolymer contained in the actinic ray curable resin is represented by the following general formula (1):

The monomer unit represented by these is included.

In the general formula (1), R ₁ and R ₂ each independently represent a hydrogen atom or a methyl group, and R ₃ is a hydrogen atom, an alkyl group, or an aryl group. The alkyl group for R ₃ is preferably an alkyl group having up to 7 carbon atoms such as a methyl group or an ethyl group. Moreover, as the aryl group of R _3, an aryl group having up to 10 carbon atoms such as a phenyl group and a naphthyl group is preferable. However, when R ₂ is a methyl group, R ₃ is a hydrogen atom.

In the general formula (1), L represents a divalent linking group, for example, —CH ₂ —CH (OH) —CH ₂ —O—, —OCH ₂ CH (OH) CH ₂ OCO—, — OCH ₂ CH ₂ OCONH—R ₄ —NHCOOCH ₂ — (wherein R ₄ is a p-phenylene group), —OCH ₂ CH ₂ OCOCH ₂ CH ₂ COOCH ₂ —, —OCH ₂ CH ₂ OCO—R ₅ — COOCH ₂ — (wherein R ₅ is an o-phenylene group) and the like. Among these, L is preferably -CH ₂ -CH (OH) is -CH ₂ -O-.

  The monomer represented by the general formula (1) is a monomer having a carboxyl group, α, β-unsaturated carboxylic acid (for example, acrylic acid, methacrylic acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride Acid, etc.) once copolymerized with an anhydride such as maleic anhydride, and then hydrolyze the anhydride with an alcohol such as methanol, ethanol, propanol, or butanol on one side of the carboxylic acid, and then carboxylic acid on one side It can be obtained by adding a long-chain alkyl group to the portion, or by a polymer reaction of an active group in the polymer such as a hydroxyl group or an amino group with a dicarboxylic acid or an acid anhydride.

  The unsaturated group-containing acrylic copolymer preferably contains 0.01 to 50% by mass of the monomer unit represented by the general formula (1) in the molecule, more preferably 0.1 to 20%. % By mass. When the monomer unit represented by the general formula (1) is within the above range, it is possible to efficiently synthesize an unsaturated group-containing acrylic copolymer and obtain a protective layer having high surface strength. it can.

  Other monomer units to be copolymerized with the monomer unit represented by the general formula (1) include monomers having an aromatic hydroxyl group, monomers having an aliphatic hydroxyl group, monomers having an aminosulfonyl group, and monomers having a sulfonamide group. , Α, β-unsaturated carboxylic acids, substituted or unsubstituted alkyl acrylates, substituted or unsubstituted alkyl methacrylates, acrylamides or methacrylamides, monomers containing fluorinated alkyl groups, vinyl ethers, vinyl esters, styrenes , Vinyl ketones, olefins, N-vinyl pyrrolidone, N-vinyl carbazole, 4-vinyl pyridine, a monomer having a cyano group, a monomer having an amino group, and the like.

  Moreover, it is preferable that the acid value of an unsaturated group containing acrylic copolymer is 5-500 mgKOH / g, More preferably, it is 10-150 mgKOH / g. By using an unsaturated group-containing acrylic copolymer having an acid value in the above range, adhesion with an intermediate layer and an adhesive layer described later can be improved, and a protective layer having high surface strength can be obtained. In the present invention, the “acid value” means the number of milligrams of potassium hydroxide necessary for neutralizing free fatty acids contained in 1 g of the polymer, and is measured by a method according to JIS-K-2501. be able to. The acid value of the polymer can be adjusted as appropriate by adjusting the ratio of monomer components constituting the polymer.

  Moreover, the mass average molecular weight of the unsaturated group-containing acrylic copolymer is preferably in the range of 3000 to 100,000, more preferably 10,000 to 80,000. When the molecular weight is less than 10,000, there is a tendency of heat resistance deterioration or chemical resistance deterioration and scratch strength deterioration. On the other hand, when it is larger than 100,000, gelation reaction tends to occur during storage, and stability becomes a problem. In the present invention, “mass average molecular weight” means a value measured by gel permeation chromatography using polystyrene as a standard substance, and can be measured by a method based on JIS-K-7252-1.

  The unsaturated group-containing acrylic copolymer is preferably contained in an actinic ray curable resin in an amount of 10 to 80% by mass, more preferably 20 to 70% by mass, and still more preferably 20 to 50% by mass. It is.

  The other monomer contained in the actinic ray curable resin can be used without particular limitation as long as it is a monomer or oligomer having at least one polymerizable double bond in one molecule. For example, 2-ethylhexyl acrylate, 2-hydroxypropyl acrylate, glycerol acrylate, tetrahydrofurfuryl acrylate, phenoxyethyl acrylate, nonylphenoxyethyl acrylate, tetrahydrofurfuryloxyethyl acrylate, tetrahydrofurfuryloxyhexanolide acrylate, 1,3- Monofunctional acrylates such as acrylate of ε-caprolactone adduct of dioxane alcohol, 1,3-dioxolane acrylate, or methacrylic acid, itaconic acid, crotonic acid in which these acrylates are replaced with methacrylate, itaconate, crotonate, maleate, Maleate esters such as ethylene glycol diacrylate, triethylene glycol diacryl , Pentaerythritol diacrylate, hydroquinone diacrylate, resorcinol diacrylate, hexanediol diacrylate, neopentyl glycol diacrylate, tripropylene glycol diacrylate, hydroxypentylate neopentyl glycol diacrylate, neopentyl glycol adipate diacrylate, hydroxy Diacrylate of ε-caprolactone adduct of neopentyl glycol pivalate, 2- (2-hydroxy-1,1-dimethylethyl) -5-hydroxymethyl-5-ethyl-1,3-dioxane diacrylate, tricyclode Candimethylol acrylate, ε-caprolactone adduct of tricyclodecane dimethylol acrylate, diglycidyl ester of 1,6-hexanediol Difunctional acrylates such as diacrylate of ter, or methacrylic acid, itaconic acid, crotonic acid, maleic acid ester in which these acrylates are replaced by methacrylate, itaconate, crotonate, maleate, such as trimethylolpropane triacrylate, ditrimethylol Propane-tetraacrylate, trimethylolethane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, ε-caprolactone adduct of dipentaerythritol hexaacrylate, Pyrogallol triacrylate, propionic acid, dipentaerythritol Multifunctional acrylic ester acid such as triacrylate, propionic acid / dipentaerythritol tetraacrylate, hydroxypivalyl aldehyde modified dimethylolpropane triacrylate, or methacrylic acid, itacon in which these acrylates are replaced with methacrylate, itaconate, crotonate, maleate Acid, crotonic acid, maleic acid ester, phosphazene monomer, triethylene glycol, isocyanuric acid EO-modified diacrylate, isocyanuric acid EO-modified triacrylate, dimethylol tricyclodecane diacrylate, trimethylolpropane acrylic acid benzoate, alkylene Examples include glycol type acrylic acid modified, urethane modified acrylate and the like.

  Among the above, acrylic acid ester and methacrylic acid ester compounds can be particularly preferably used. Among these compounds, one kind or a mixture of two or more kinds can be used. In addition, as a compound capable of addition polymerization or crosslinking, a so-called prepolymer in which acrylic acid or methacrylic acid is introduced into an oligomer having an appropriate molecular weight to impart photopolymerizability can be suitably used. These may be used alone or in combination with two or more prepolymers, or may be used in combination with the above-mentioned monomers.

  Examples of prepolymers include adipic acid, trimellitic acid, maleic acid, phthalic acid, terephthalic acid, hymic acid, malonic acid, succinic acid, glutaric acid, itaconic acid, pyromellitic acid, fumaric acid, glutaric acid, pimelic acid, sebacin Polybasic acids such as acid, dodecanoic acid, tetrahydrophthalic acid, and ethylene glycol, propylene glycol, diethylene glycol, propylene oxide, 1,4-butanediol, triethylene glycol, tetraethylene glycol, polyethylene glycol, glycerin, trimethylolpropane , Polyester ester obtained by introducing (meth) acrylic acid into polyester obtained by combining polyhydric alcohols such as pentaerythritol, sorbitol, 1,6-hexanediol, 1,2,6-hexanetriol Relates such as bisphenol A, epichlorohydrin, (meth) acrylic acid, and epoxy acrylates in which (meth) acrylic acid is introduced into an epoxy resin such as phenol novolac, epichlorohydrin, (meth) acrylic acid, such as ethylene glycol adipine Acid / tolylene diisocyanate / 2-hydroxyethyl acrylate, polyethylene glycol / tolylene diisocyanate / 2-hydroxyethyl acrylate, hydroxyethylphthalyl methacrylate / xylene diisocyanate, 1,2-polybutadiene glycol / tolylene diisocyanate / 2-hydroxyethyl acrylate , Trimethylolpropane, propylene glycol, tolylene diisocyanate, 2-hydroxyethyl acrylate In addition, urethane acrylate in which (meth) acrylic acid is introduced into urethane resin, for example, silicone resin acrylates such as polysiloxane acrylate, polysiloxane diisocyanate, 2-hydroxyethyl acrylate, etc., and (meth) acryloyl in oil-modified alkyd resin Examples thereof include alkyd-modified acrylates having a group introduced therein, and spirane resin acrylates.

  The monomer oligomer or prepolymer having one or more polymerizable double bonds in the molecule may be contained in the actinic ray curable resin in a proportion of 20 to 90% by mass.

  The actinic ray curable resin layer is a known coating such as a roll coat, reverse roll coat, gravure coat, reverse gravure coat, bar coat, rod coat, etc., which is a coating liquid comprising a composition containing an actinic ray curable resin as described above. By a means, it can form by apply | coating on a mold release layer or a peeling layer, forming a coating film, and making it harden | cure by the method as mentioned later.

  The thickness of the actinic ray curable resin layer is preferably 5 μm to 20 μm. If the thickness of the actinic radiation curable resin layer 4 is less than 5 μm, sufficient hard coat performance may not be imparted even if the protective layer is transferred to the transfer target, and if the thickness is greater than 20 μm, the protective layer There are cases where the foil breakage becomes worse at the time of transfer and the transferability is lowered.

  The actinic ray curable resin layer may contain fine particles in addition to the above-described resin. In the present invention, it is possible to improve both the transferability and the surface strength of the protective layer transfer sheet by two-time exposure as described later. However, since the breaking strength of the actinic ray curable resin layer is improved, When the light-curing resin layer has a certain thickness, the foil breakage may deteriorate during transfer of the protective layer, and transferability may be reduced. By including fine particles in the actinic ray curable resin layer, the breakability is improved even when the thickness of the actinic ray curable resin layer exceeds 20 μm, and both the transferability and surface strength of the protective layer transfer sheet are improved. Can be improved.

  The fine particles contained in the actinic radiation curable resin layer preferably have an average particle diameter in the range of 0.05 μm to 5 μm. If the average particle size is less than 10 nm, sufficient breakability is not improved, and a large amount of fine particles is required to improve the breakability, which may cause a problem in the appearance of the resin layer, while 5 μm Exceeding may cause agglomeration of fine particles in the actinic ray curable resin layer, resulting in poor appearance. The average particle diameter of the fine particles is more preferably 0.1 to 1 μm. The “average particle size” means the volume average particle size, and is measured by a known method using a particle size distribution / particle size distribution measuring device (for example, Nanotrack particle size distribution measuring device, manufactured by Nikkiso Co., Ltd.). can do.

  The above-mentioned fine particles can be used without particular limitation even if they are inorganic type such as silica, alumina, zinc oxide, or organic type such as resin. It is preferable to use organic fine particles that facilitate easy dispersion of fine particles.

  Examples of the organic fine particles include polystyrene resins, crosslinked polymethyl methacrylate, cellulose resins, polyester resins, polyamide resins, polyacrylate resins, polyacryl resins, polycarbonate resins, polyurethane resins, polyolefin resins, In addition to polyvinyl acetal resins, fluorine resins, polyimide resins, etc., fine particles made of polyhydric alcohols such as polyethylene glycol can be mentioned. Among the above, acrylic resin crosslinked fine particles, styrene resin crosslinked fine particles, silicone resin crosslinked fine particles, and MS (methyl methacrylate / styrene copolymer) crosslinked fine particles can be suitably used. Further, polystyrene fine particles using fine particles made of an acrylic resin for the core, and conversely polyacryl fine particles using fine particles made of a styrene resin for the core can be used. In addition, when the core is a styrene resin fine particle, the shell acrylic resin may have a functional group. For example, polymethylolpropane tri (meth) acrylate, hexanediol (meth) acrylate, polypropylene glycol di (meth) acrylate , Diethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, bisphenol F EO modified di (meth) acrylate, bisphenol A EO modified di (meth) acrylate, trimethylolpropane tri (meth) acrylate, dipentaerythritol penta ( (Meth) acrylate, isocyanuric acid EO-modified di (meth) acrylate, isocyanuric acid EO-modified tri (meth) acrylate, polypropylene glycol di (meth) acrylate, trimethylo Rupropane PO-modified tri (meth) acrylate, trimethylolpropane EO-modified tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 1,6- You may use the microparticles | fine-particles which formed the shell with reaction products, such as polyfunctional compounds, such as hexanediol di (meth) acrylate and neopentyl glycol di (meth) acrylate, and (meth) allylate. As the above-mentioned fine particles, commercially available particles may be used, for example, Sekisui Chemical Co., Ltd. Techpolymer series, Momentive Performance Materials Japan GK XC99-A8808, etc. Can do.

  The fine particles described above are preferably contained in the actinic ray curable resin layer in a proportion of 0.01 to 30% by mass. When the content of the fine particles is less than 0.01% by mass, the foil breakage may be deteriorated when the thickness of the actinic ray curable resin layer is thick. On the other hand, when the content exceeds 30% by mass, the actinic ray curable resin layer is deteriorated. In some cases, the strength of the resin is reduced, and sufficient hard coat performance cannot be imparted. A more preferable content of the fine particles is 0.5 to 20% by mass.

  Next, the intermediate layer provided on the actinic ray curable resin layer will be described. The intermediate layer 5 has a function of improving adhesion between the actinic ray curable resin layer 4 and the adhesive layer 6. As a material constituting the intermediate layer, for example, vinyl chloride resin, polyester resin, acrylic resin, polyvinyl acetal resin, polyvinyl alcohol, polycarbonate, cellulose resin, styrene resin, urethane resin, urethane acrylate resin, Resins such as amide resin, urea resin, epoxy resin, phenoxy resin, polycaprolactone resin, polyacrylonitrile resin, styrene resin (styrene block copolymer (SBC)), olefin resin (TP), urethane resin (TPU) And thermoplastic elastomers such as polyester (TPEE), polyamide (TPAE), 1,2-polybutadiene, vinyl chloride (TPVC), fluorine, ionomer resin, chlorinated polyethylene, and silicone. Specific examples of the thermoplastic elastomer include SEBS resins, SEPS resins, and modified products thereof described in the 1996 edition of “12996 Chemical Products” (Chemical Industry Daily). The above-described resins may be used alone or in combination of two or more.

  Among the above-described resins, thermoplastic resins made of polystyrene and polyolefin block polymers, polyvinyl butyral resins, and the like are preferable. As a polyvinyl butyral resin, SRECIK BH-3, BX-1, BX-2, BX-5, BX-55, BH-S, BL-S manufactured by Sekisui Chemical Co., Ltd., manufactured by Denki Kagaku Kogyo Co., Ltd. Commercially available products such as Denkabutyral # 4000-2, # 5000-A, # 6000-EP may be used. These polybutyral resins are not particularly limited in the degree of polymerization before thermosetting. Further, from the viewpoint of film strength, a thermosetting compound may be added to the above-described resin. Specifically, an isocyanate curing agent, an epoxy curing agent, or the like can be used, and the thermosetting conditions are preferably 50 to 90 ° C. and 1 to 72 hours.

  The intermediate layer may contain additives such as an ultraviolet absorber, an antioxidant, and a light stabilizer. These additives need to be added to such an extent that the function of the intermediate layer is not impaired. Specifically, the content of the additive is preferably 0.05 to 20% by mass, more preferably 0.05% to 10% by mass with respect to 100% by mass of the total solid content of the resin.

  The intermediate layer may contain the fine particles described above. By containing fine particles, it is possible to obtain a protective layer transfer sheet that is further excellent in transferability and surface strength of the protective layer transfer sheet.

  The ultraviolet absorber added to the intermediate layer is not particularly limited as long as it functions as an ultraviolet absorber for dye images and can be thermally transferred. For example, JP-A-59-158287, 63-74666, and 63. -145089, 59-196292, 62-229594, 63-122596, 61-283595, JP-A-1-204788, and the like, and Known compounds can be used to improve the image durability in photographs and other image recording materials. Specific examples include salicylic acid type, benzophenone type, benzotriazole type, and cyanoacrylate type. For example, Tinuvin P, Tinuvin 123, 234, 320, 326, 327, 328, 312, 315, 384, 400 (manufactured by Ciba Geigy) ), Sumisorb-110, 130, 140, 200, 250, 300, 320, 340, 350, 400 (manufactured by Sumitomo Chemical Co., Ltd.), MarkLa-32, 36, 1413 (manufactured by Adeka Gas Chemical Co., Ltd.) A commercially available product such as can be suitably used. A pendant polymer having a benzophenone derivative or the like in the side chain is also preferably used. In addition, inorganic fine particles having absorption in the ultraviolet region, ultrafine metal oxide powder dispersants and the like can also be used. Examples of inorganic fine particles include titanium oxide, zinc oxide, and silicon compounds. Examples of the ultrafine metal oxide powder dispersant include ultrafine zinc oxide powder, ultrafine titanium oxide powder, and the like, water or alcohol mixed liquids or various oil dispersion media, surfactants, water-soluble polymers, and solvent-soluble polymers. And those made using a dispersing agent such as

  Examples of the antioxidant added to the intermediate layer include the antioxidants described in JP-A-59-182785, JP-A-60-130735, JP-A-1-127387, and the like. Known compounds can be used to improve the image durability of the image recording material. Specific examples include primary antioxidants such as phenols, monophenols, bisphenols, and amines, or secondary antioxidants such as sulfurs and phosphoruss. For example, Sumizer BBM-S, BHT, BP -76, MDP-S, GM, WX-R, BP-179, GA, TPM, TP-D, TNP (manufactured by Sumitomo Chemical Co., Ltd.), Irganox-245, 259, 565, 1010, 1035, 1076, Commercially available products such as 1081, 1098, 3114 (manufactured by Ciba Geigy), MarkAQ-20, AO-30, AO-40 (manufactured by Adeka Argus Chemical Co., Ltd.) can be suitably used.

  As the light stabilizer added to the intermediate layer, JP-A-59-158287, JP-A-63-74666, JP-A-63-145089, JP-A-59-196292, JP-A-62-229594, The compounds described in JP-A-63-122596, JP-A-61-283595, JP-A-1-204788, and the like, and compounds known as those for improving image durability in photographs and other image recording materials are used. Can be mentioned. Specific examples include hindered amines, such as Tinuvin 622LD, 144, Chimassob 944 LD (manufactured by Ciba Geigy), Sanol LS-770, LS-765, LS-292, LS-2626, LS-114, LS-774. (Sankyo Co., Ltd.), Mark LA-62, LA-67, LA-63, LA-68, LA-82, LA-87 (Adeka Argus Chemical Co., Ltd.) and other commercially available products are preferably used. it can.

  The adhesive layer 6 provided on the intermediate layer 5 can be applied with a heat-adhesive adhesive that is melted or softened by heat to bond, for example, ionomer resin, acid-modified polyolefin resin, ethylene- (meth) acrylic acid copolymer Coalescence, ethylene- (meth) acrylic acid ester copolymer, polyester resin, polyamide resin, vinyl resin, acrylic / methacrylic (meth) acrylic resin, acrylic ester resin, maleic acid resin, Butyral resin, alkyd resin, polyethylene oxide resin, phenolic resin, urea resin, melamine resin, melamine-alkyd resin, cellulose resin, polyurethane resin, polyvinyl ether resin, silicone resin, rubber resin, etc. can be applied, These resins are used alone or in combination. The resin of these adhesive layers is preferably a vinyl resin, an acrylic resin, a butyral resin, or a polyester resin in terms of adhesive strength. More preferred are vinyl resins, acrylic resins, ethylene- (meth) ethyl acrylate copolymers, and acrylate ester copolymers.

  The adhesive layer may contain the fine particles described above. By containing fine particles, it is possible to obtain a protective layer transfer sheet that is further excellent in transferability and surface strength of the protective layer transfer sheet.

  The thickness of the adhesive layer to be formed is usually about 0.05 to 5 μm, preferably 0.1 to 3 μm. If the thickness of the adhesive layer is less than 0.05 μm, the adhesive force with the transfer object may be insufficient and dropout may occur. On the other hand, if the thickness exceeds 5 μm, the adhesive effect does not change, resulting in an increase in cost. At the same time, the heat of the thermal head when transferring the protective layer transfer sheet is wasted.

<Method for producing protective layer transfer sheet>
Next, a method for producing the above protective layer transfer sheet will be described. FIG. 2 is a schematic process diagram showing each process of the method for producing a protective layer transfer sheet according to the present invention. The method of the protective layer transfer sheet according to the present invention comprises laminating a release layer and / or release layer 2 on a support 1 and containing an actinic ray curable resin on the release layer and / or release layer 2. The coating solution 3 is applied to form the coating film 3, and the coating film 3 is irradiated with actinic rays at least twice to form the actinic ray curable resin layer 4. A protective layer transfer sheet comprising at least an actinic ray curable resin layer 4 provided on a support 1 via a release layer and / or a release layer 2 is produced. Hereinafter, each step will be described.

  In the method for producing a protective layer transfer sheet according to the present invention, first, a support 1 is prepared as shown in FIG. Next, a release layer and / or a release layer 2 are laminated on the support 1 (FIG. 1B). Next, a coating liquid containing the above-mentioned actinic ray curable resin is applied onto the release layer and / or the release layer 2 to form a coating film 3 (FIG. 1C). As described above, the coating film 3 is cured by irradiation with actinic rays, whereby the actinic ray curable resin layer 4 constituting the protective layer to be transferred is formed. The coating film is formed by releasing the coating liquid composed of the composition containing the above-mentioned actinic ray curable resin by known means such as roll coating, reverse roll coating, gravure coating, reverse gravure coating, bar coating, rod coating, and the like. It can form by apply | coating on a layer or a peeling layer. The coating film may be dried or aged at a temperature of 30 ° C. to 120 ° C. before irradiation with actinic rays described later.

  Subsequently, when the coating film 3 made of the actinic ray curable resin composition obtained as described above is irradiated with actinic rays to polymerize and cure the resin composition, the actinic rays are applied at least twice or more. Irradiation forms the actinic ray curable resin layer 4. That is, the resin is semi-cured by the first actinic ray irradiation (FIG. 1D), and then the actinic ray curable resin layer 4 is formed by irradiating the semi-cured resin 3 ′ with the actinic ray for the second time. (FIG. 1 (e)).

  The inventors of the present invention form an actinic ray curable resin layer by at least two actinic ray irradiations as described above instead of forming an actinic ray curable resin layer by one actinic ray irradiation. Thus, it was found that both transferability and surface strength of the obtained protective layer transfer sheet can be improved. The reason for this is not clear, but is considered as follows. That is, by leaving the resin in a semi-cured state without being completely cured by the first irradiation with actinic rays, the release layer and / or the release layer and the coating film (consisting of an actinic ray curable resin composition). At the interface with the film, a semi-cured resin (for example, an oligomer or the like) enters the release layer and / or the release layer. In this state, the second actinic ray is irradiated to completely cure the resin, thereby improving the adhesion between the release layer and / or the release layer and the formed actinic ray curable resin layer. Since the actinic ray curable resin can be completely cured by the second actinic ray irradiation, a desired surface strength can be obtained. On the other hand, when the actinic ray curable resin is cured by a single actinic ray irradiation until the desired surface strength is reached, an actinic ray curable resin oligomer or the like is formed on the release layer and / or the release layer. It is considered that the adhesiveness is not improved because there is no time for the ink to enter, and as a result, the transferability becomes insufficient. The above is only an assumption, and the present invention is not bound by the above theory.

  Irradiation of actinic rays is preferably performed intermittently two times or more, rather than continuously twice or more. After the first actinic ray irradiation, the second actinic ray irradiation is performed in a separate step. It is more preferable. In the case where the first and second actinic ray irradiation is performed intermittently, for example, after the coating film 3 is formed on the production line (FIG. 2 (c)), the first actinic ray irradiation is subsequently performed (see FIG. 2). 2 (d)), the second irradiation of active light (FIG. 2 (e)) can be performed on the same production line. In addition, when performing the second actinic ray irradiation in a separate process, in a state where the resin is semi-cured by the first actinic ray irradiation (the state of FIG. 2 (d)), it is once wound into a roll shape, It may be supplied to the second actinic ray irradiation step in a roll form, and the actinic ray may be irradiated for the second time to the semi-cured resin (coating film) (FIG. 2 (e)).

As described above, when actinic ray irradiation is performed twice or more in a separate process, the actinic ray is applied so that the irradiation energy at the second irradiation is higher than the irradiation energy at the first irradiation. It is preferable to form an actinic ray curable resin layer by irradiation. For example, irradiation with ultraviolet rays can be performed as the first active light irradiation, and irradiation with ultraviolet rays or an electron beam can be performed as the second and subsequent active light irradiations. In this case, 10 to 350 mW / cm ² is preferable, and more preferably 10 to 240 mW / cm ² of the peak illuminance of the ultraviolet when the first ultraviolet irradiation is performed. Moreover, 10-200 mj / cm < ² > is preferable and, as for the integrated exposure amount in the time of the 1st ultraviolet irradiation, More preferably, it is 10-130 mj / cm < ² >. By irradiating ultraviolet rays under the irradiation conditions as described above, the actinic ray curable resin can be kept in a semi-cured state without being completely cured.

When ultraviolet rays are used for the second and subsequent actinic ray irradiation, the actinic ray curable resin is completely cured by irradiating the ultraviolet rays with an integrated exposure amount of 50 to 500 mj / cm ² , preferably 50 to 400 mj / cm ^2. Can do. In addition, when an electron beam is used for the second and subsequent actinic ray irradiation, the actinic ray curable resin is completely cured by irradiating the electron beam with an irradiation energy of 50 to 300 kGy, preferably 100 to 250 kGy. Can do. As described above, by increasing the irradiation energy of the second and subsequent ultraviolet irradiations as compared with the first ultraviolet irradiation, a protective layer transfer sheet having further excellent transferability and surface strength can be obtained.

  For the irradiation of ultraviolet rays, a conventionally known ultraviolet irradiation device can be used. For example, various types such as a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc, a xenon arc, a metal halide lamp, an electrodeless ultraviolet lamp, and an LED are used without limitation. be able to. In addition, the electron beam irradiation may be performed using either a high energy electron beam irradiation apparatus that irradiates an electron beam with an energy of 100 keV to 300 keV or a low energy electron beam irradiation apparatus that irradiates an electron beam with an energy of 100 keV or less. Moreover, the irradiation method may be either a scanning type or a curtain type irradiation device.

  As shown in FIG. 2 (f), the second and subsequent actinic ray irradiations may be performed before forming the adhesive layer 6 described later (FIG. 2 (f)), but as shown in FIG. By the first actinic ray irradiation, the coating film 3 (actinic ray curable resin) is put into a semi-cured state 3 ′ (FIG. 3D), and is adhered onto the coating film 3 ′ as described later. After forming the layer 6 (FIG. 3 (e)), the second and subsequent actinic ray irradiations may be performed (FIG. 3 (f)), and as shown in FIG. After the coating film (actinic ray curable resin) is in a semi-cured state 3 ′ (FIG. 4D), the intermediate layer 5 and the adhesive layer 6 are formed on the coating film 3 ′ (FIG. 4 (e)) Second and subsequent actinic ray irradiation may be performed (FIG. 4 (f))).

  The second and subsequent actinic ray irradiations are preferably performed after 2 hours or more have passed since the first actinic ray irradiation, more preferably after 12 hours. By performing the second and subsequent actinic ray irradiation after 12 hours or more have passed since the first actinic ray irradiation, a protective layer transfer sheet having even better transferability and surface strength can be obtained.

  In the present invention, after forming the actinic radiation curable resin layer 4 as described above, the adhesive layer 6 is formed on the actinic radiation curable resin layer 4 (FIG. 1 (f)). The actinic ray curable resin layer 4 and the adhesive layer 6 of the protective layer transfer sheet 10 are peeled off from the release layer 2 and transferred as a protective layer 7 to a transfer target (not shown). These are provided to improve the adhesion between the transfer target and the protective layer 7.

  When the intermediate layer 5 is formed by actinic ray irradiation, as shown in FIGS. 3 and 4, the intermediate layer forming coating solution is applied onto the semi-cured coating film (active light curable resin) 3 ′. The actinic ray curable resin layer 4 and the intermediate layer 5 may be simultaneously formed by irradiating actinic rays for the second time, thereby reducing the number of steps, and thus producing a protective layer transfer sheet. Cost can be reduced.

  When the protective layer 7 is transferred to a transfer target (not shown) using the protective layer transfer sheet 10 according to the present invention, when the actinic ray curable resin layer 4 (the intermediate layer 5 and the adhesive layer 6 are provided) The actinic ray curable resin layer 4, the intermediate layer 5, and the adhesive layer 6) are transferred as a protective layer 7 to the transfer target.

  The material to be transferred is not particularly limited as long as it requires durability such as wear resistance and plasticizer resistance. For example, natural fiber paper, coated paper, tracing paper, heat during transfer, and the like. It may be any plastic film, glass, metal, ceramics, wood, cloth or dye-receptive medium that does not deform. Further, since an IC card or the like is usually required to have a design property and a security property, a printing layer, a hologram layer, and the like are generally provided on a surface to which a protective layer of a transfer target is transferred.

  As a method for transferring the protective layer onto the transfer material using the protective layer transfer sheet according to the present invention, a known transfer method may be used. For example, hot stamping by hot stamping (foil stamping), entire surface or stripe by hot rolls. A known method such as transfer or a thermal printer (also referred to as a thermal transfer printer) using a thermal head (thermal printing head) can be applied. Preferably, front transfer is performed by a hot roll.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these Examples.

Synthesis example 1
In a three-necked flask under nitrogen flow, 58 parts of methyl methacrylate, 30 parts of benzyl methacrylate and 12 parts of methacrylic acid are added, and further 500 parts of ethanol and 3 parts of α, α'-azobisisobutyronitrile are added. The reaction was performed in an oil bath at 80 ° C. in a nitrogen stream for 6 hours. Thereafter, 3 parts of triethylammonium chloride and 0.6 part of glycidyl methacrylate were added and reacted for 3 hours to obtain an acrylic copolymer 1.

  The obtained acrylic copolymer 1 had a mass average molecular weight of 21,000 and an acid value of 62.9 mgKOH / g. The unsaturated group content in the acrylic copolymer 1 was 0.6% by mass.

Synthesis example 2
In a three-necked flask under a nitrogen stream, 40 parts of methyl methacrylate, 30 parts of benzyl methacrylate, 20 parts of cyclohexyl acrylate and 12 parts of methacrylic acid are added, and further 500 parts of ethanol and α, α'-azobisisobutyronitrile. 3 parts were added and reacted in an oil bath at 80 ° C. in a nitrogen stream for 6 hours. Thereafter, 3 parts of triethylammonium chloride and 0.6 part of glycidyl methacrylate were added and reacted for 3 hours to obtain an acrylic copolymer 2.

  The obtained acrylic copolymer 2 had a mass average molecular weight of 22,000 and an acid value of 63.1 mgKOH / g. The unsaturated group content in the acrylic copolymer 2 was 0.6% by mass.

Synthesis example 3
In a three-necked flask under a nitrogen stream, 60 parts of methyl methacrylate, 20 parts of benzyl methacrylate and 20 parts of methacrylic acid are added, and 500 parts of ethanol and 3 parts of α, α'-azobisisobutyronitrile are added. The reaction was performed in an oil bath at 80 ° C. in a nitrogen stream for 6 hours. Thereafter, 10 parts of triethylammonium chloride and 10.0 parts of glycidyl methacrylate were added and reacted for 3 hours to obtain an acrylic copolymer 3.

  The obtained acrylic copolymer 3 had a mass average molecular weight of 20000 and an acid value of 15 mgKOH / g. Moreover, unsaturated group content in the acryl-type copolymer 3 was 10 mass%.

Synthesis example 4
In a three-necked flask under nitrogen flow, 58 parts of methyl methacrylate, 30 parts of benzyl methacrylate and 12 parts of methacrylic acid are added, and further 500 parts of ethanol and 3 parts of α, α'-azobisisobutyronitrile are added. The acrylic copolymer 4 was obtained by reacting in an oil bath at 80 ° C. for 6 hours in a nitrogen stream.

  The obtained acrylic copolymer 4 had a mass average molecular weight of 18000 and an acid value of 63.4 mgKOH / g. The unsaturated group content in the acrylic copolymer 4 was 0% by mass.

Synthesis example 5
In a three-necked flask under nitrogen flow, 58 parts of methyl methacrylate, 30 parts of benzyl methacrylate and 12 parts of methacrylic acid are added, and further 500 parts of ethanol and 3 parts of α, α'-azobisisobutyronitrile are added. The reaction was performed in an oil bath at 80 ° C. in a nitrogen stream for 6 hours. Thereafter, 3 parts of triethylammonium chloride and 60.0 parts of glycidyl methacrylate were added and reacted for 3 hours to obtain an acrylic copolymer 5. However, it was gelled and could not be used.

Example 1
Using a polyethylene terephthalate (PET) film (Lumirror, manufactured by Toray Industries, Inc.) having a thickness of 25 μm as a support, a release layer coating liquid having the following composition is applied to one surface thereof by gravure coating, and the thickness after drying Was applied to a thickness of 1.5 μm and dried to form a release layer.
<Composition of release layer coating solution>
Norbornene resin (Nippon Synthetic Rubber Co., Ltd., Arton G) 40 parts Acrylic polyol resin 10 parts (Trade name Thermolac SU-100A, manufactured by Soken Chemical Co., Ltd.)
Solvent (methyl ethyl ketone: toluene = 2: 8) 50 parts

Next, an actinic ray curable resin coating liquid A having the following composition is applied on the formed release layer by gravure coating so that the thickness after drying becomes 6 μm and dried to form a coating film. did.
<Actinic ray curable resin coating liquid A composition>
40 parts of urethane oligomer (trade name NK Oligo A-9300, manufactured by Shin-Nakamura Chemical Co., Ltd.)
25 parts of polyfunctional oligomer (trade name NK Oligo UA-122P, manufactured by Shin-Nakamura Chemical Co., Ltd.)
Acrylic copolymer 1 30 parts Photopolymerization initiator 5 parts (trade name Irgacure 907, manufactured by Ciba Specialty Chemicals)
200 parts of methyl ethyl ketone

The coating film formed as described above was irradiated with ultraviolet rays under the following irradiation conditions using a UV exposure device (Fusion UV, F600V, LH10 lamp, H bulb, reflecting mirror is a cold type). The peak illuminance and the integrated exposure amount were measured using a microcure model MC-2 with a UV illuminance meter microcure data reader manufactured by Fusion UV Systems Japan. The peak illuminance and integrated exposure during UV irradiation can be changed by changing the distance (mm) between the light source and the substrate, and also changing the lamp light source output (%) and the conveyance speed (m / min). Adjusted by.
Peak illuminance: 50 mW / cm ²
Integrated exposure: 50 mj / cm ²

After the first ultraviolet irradiation as described above, it was stored at room temperature for 5 days. After that, the actinic ray curable resin layer was formed by irradiating the coating film irradiated with ultraviolet rays with an electron beam using a variable shaping type electron beam drawing apparatus as the second actinic ray irradiation to cure the resin. Note that the electron beam irradiation conditions were the doses shown in Table 1. The electron beam dose was adjusted by changing the acceleration voltage (kV), beam current (A / cm ² ), and conveyance speed (m / min).

Next, on the actinic ray curable resin layer formed as described above, an intermediate layer coating solution having the following composition was applied by gravure coating so that the thickness after drying was 0.5 μm, and then 50 ° C. An intermediate layer was formed by aging for 24 hours.
<Intermediate layer coating solution composition A>
8 parts of polyvinyl butyral resin (trade name BX-1, ELEX B series, manufactured by Sekisui Chemical Co., Ltd.)
90 parts of methyl ethyl ketone Hardener (Coronate HX, manufactured by Nippon Polyurethane Co., Ltd.) 2 parts

Subsequently, on the intermediate layer formed as described above, an adhesive layer coating liquid having the following composition was applied by gravure coating and dried so that the thickness after drying was 1.0 μm. Thus, a protective layer transfer sheet having a layer structure of support / active light curable resin layer / intermediate layer / adhesive layer was obtained.
<Adhesive layer coating solution composition>
Vinyl chloride-vinyl acetate copolymer 20 parts Acrylic resin 10 parts Solvent (ethyl acetate: toluene = 2: 5) 70 parts

Example 2
In Example 1, a protective layer transfer sheet was prepared in the same manner as in Example 1 except that the irradiation conditions of the electron beam on the coating film coated with the actinic ray curable resin coating liquid A were changed to the conditions shown in Table 1. Was made.

Examples 3-4
In Example 1, instead of the electron beam irradiation which is the second actinic ray irradiation, ultraviolet irradiation by a high-pressure mercury lamp was performed, and the standing time until the second actinic ray irradiation was changed to the time shown in Table 1. Produced a protective layer transfer sheet in the same manner as in Example 1.

Example 5
In Example 3, immediately after the coating film was irradiated with ultraviolet rays, the intermediate layer coating solution was applied onto the coating layer, and then the adhesive layer coating solution was applied onto the intermediate layer coating solution. A protective layer transfer sheet was produced in the same manner as in Example 3 except that the coating film was subjected to the second ultraviolet irradiation under the irradiation conditions shown in Table 1 via the layer and the adhesive layer.

Example 6
In Example 5, a protective layer transfer sheet was produced in the same manner as in Example 5 except that the acrylic copolymer 1 in the used actinic radiation curable resin coating liquid A was replaced with the acrylic copolymer 2. did.

Example 7
In Example 5, a protective layer transfer sheet was produced in the same manner as in Example 5 except that the acrylic copolymer 1 in the used actinic radiation curable resin coating liquid A was replaced with the acrylic copolymer 3. did.

Example 8
In Example 5, after applying the intermediate layer coating liquid on the coating film immediately after the coating film was irradiated with ultraviolet rays, the coating film was immediately subjected to the second ultraviolet irradiation through the intermediate layer, and then 50 A protective layer transfer sheet was produced in the same manner as in Example 5 except that aging was performed at ° C for 24 hours, and then an adhesive layer was formed on the intermediate layer.

Example 9
In Example 8, a protective layer transfer sheet was produced in the same manner as in Example 8, except that the acrylic copolymer 1 in the used actinic radiation curable resin coating liquid A was replaced with the acrylic copolymer 2. did.

Example 10
In Example 8, a protective layer transfer sheet was prepared in the same manner as in Example 8, except that the acrylic copolymer 1 in the used actinic ray curable resin coating liquid A was replaced with the acrylic copolymer 3. did.

Example 11
A protective layer transfer sheet was prepared in the same manner as in Example 8 except that the actinic ray curable resin coating solution A used in Example 8 was replaced with the actinic ray curable resin coating solution B described below.
<Actinic ray curable resin coating composition B>
55 parts urethane oligomer (trade name NK Oligo A-9300, manufactured by Shin-Nakamura Chemical Co., Ltd.)
35 parts of polyfunctional oligomer (trade name NK Oligo UA-122P, manufactured by Shin-Nakamura Chemical Co., Ltd.)
Acrylic copolymer 1 5 parts Photopolymerization initiator 5 parts (trade name Irgacure 907, manufactured by Ciba Specialty Chemicals)
200 parts of methyl ethyl ketone

Example 12
In Example 8, the second active ray 600 mW / cm 2 peak irradiance of UV ^radiation, and the integrated except that exposure was changed to 300 mj / cm ² was produced a protective layer transfer sheet in the same manner as in Example 8 .

Example 13
In Example 12, a protective layer transfer sheet was produced in the same manner as in Example 12 except that the actinic ray curable resin coating solution A used was replaced with the actinic ray curable resin coating solution C described below.
<Actinic ray curable resin coating composition C>
40 parts of urethane oligomer (trade name NK Oligo A-9300, manufactured by Shin-Nakamura Chemical Co., Ltd.)
20 parts of polyfunctional oligomer (trade name NK Oligo UA-122P, manufactured by Shin-Nakamura Chemical Co., Ltd.)
Acrylic copolymer 1 30 parts Photopolymerization initiator 5 parts (trade name Irgacure 907, manufactured by Ciba Specialty Chemicals)
Fine particles 5 parts (Techpolymer SSX-101, average particle size 1.0 μm, material: crosslinked polymethyl methacrylate, manufactured by Sekisui Chemical Co., Ltd.)
200 parts of methyl ethyl ketone

Example 14
In Example 13, a protective layer transfer sheet was prepared in the same manner as in Example 13 except that the acrylic copolymer 1 in the used actinic radiation curable resin coating liquid C was replaced with the acrylic copolymer 2. did.

Example 15
In Example 13, a protective layer transfer sheet was produced in the same manner as in Example 13 except that the acrylic copolymer 1 in the used actinic radiation curable resin coating liquid C was replaced with the acrylic copolymer 3. did.

Example 16
In Example 12, a protective layer transfer sheet was produced in the same manner as in Example 12 except that the actinic ray curable resin coating solution A used was replaced with the actinic ray curable resin coating solution D described below.
<Actinic ray curable resin coating composition D>
40 parts of urethane oligomer (trade name NK Oligo A-9300, manufactured by Shin-Nakamura Chemical Co., Ltd.)
20 parts of polyfunctional oligomer (trade name NK Oligo UA-122P, manufactured by Shin-Nakamura Chemical Co., Ltd.)
Acrylic copolymer 1 30 parts Photopolymerization initiator 5 parts (trade name Irgacure 907, manufactured by Ciba Specialty Chemicals)
10 parts of fine particles (Techpolymer SSX-101, average particle size 1.0 μm, material: cross-linked polymethyl methacrylate, manufactured by Sekisui Chemical Co., Ltd.)
200 parts of methyl ethyl ketone

Example 17
In Example 12, a protective layer transfer sheet was produced in the same manner as in Example 12 except that the actinic ray curable resin coating liquid A used was replaced with the actinic ray curable resin coating liquid E described below.
<Actinic ray curable resin coating composition E>
40 parts of urethane oligomer (trade name NK Oligo A-9300, manufactured by Shin-Nakamura Chemical Co., Ltd.)
25 parts of polyfunctional oligomer (trade name NK Oligo UA-122P, manufactured by Shin-Nakamura Chemical Co., Ltd.)
Acrylic copolymer 1 30 parts Photopolymerization initiator 5 parts (trade name Irgacure 907, manufactured by Ciba Specialty Chemicals)
Particulate 5 parts (XC99-A8808, average particle size 0.87 μm, material: silicone resin, manufactured by Momentive Performance Materials Japan GK)
200 parts of methyl ethyl ketone

Example 18
In Example 12, a protective layer transfer sheet was produced in the same manner as in Example 12 except that the actinic ray curable resin coating solution A used was replaced with the actinic ray curable resin coating solution F described below.
<Actinic ray curable resin coating composition F>
40 parts of urethane oligomer (trade name NK Oligo A-9300, manufactured by Shin-Nakamura Chemical Co., Ltd.)
25 parts of polyfunctional oligomer (trade name NK Oligo UA-122P, manufactured by Shin-Nakamura Chemical Co., Ltd.)
Acrylic copolymer 1 30 parts Photopolymerization initiator 5 parts (trade name Irgacure 907, manufactured by Ciba Specialty Chemicals)
Fine particles 5 parts (Techpolymer MXB-8, average particle size 8.0 μm, material: cross-linked polymethyl methacrylate, manufactured by Sekisui Chemical Co., Ltd.)
200 parts of methyl ethyl ketone

Example 19
In Example 13, a protective layer transfer sheet was produced in the same manner as in Example 13 except that the standing time from the first actinic ray irradiation to the second actinic ray irradiation was changed to the time shown in Table 1.

Example 20
In Example 19, a protective layer transfer sheet was produced in the same manner as in Example 19 except that the used intermediate layer coating solution A was replaced with the following intermediate layer coating solution B.
<Intermediate layer coating solution composition B>
7.5 parts of polyvinyl butyral resin (trade name BX-1, ELEX B series, manufactured by Sekisui Chemical Co., Ltd.)
Methyl ethyl ketone 90 parts Curing agent (Coronate HX, manufactured by Nippon Polyurethane Co., Ltd.) 2 parts Fine particles 0.5 part (Techpolymer SSX-101, average particle size 1.0 μm, material: crosslinked polymethyl methacrylate, manufactured by Sekisui Chemical Co., Ltd.)

Example 21
In Example 20, a protective layer transfer sheet was produced in the same manner as in Example 20 except that the actinic ray curable resin coating solution C used was changed to the actinic ray curable resin coating solution A.

Comparative Example 1
In Example 1, a protective layer transfer sheet was produced in the same manner as in Example 1 except that the electron beam irradiation was not performed.

Comparative Example 2
In Example 5, the acrylic copolymer 1 in the used actinic radiation curable resin coating liquid A was changed to the acrylic copolymer 4, and the second ultraviolet irradiation was performed under the conditions shown in Table 1 below. A protective layer transfer sheet was produced in the same manner as in Example 5 except that the change was made.

Comparative Example 3
In Example 8, the acrylic copolymer 1 in the used actinic radiation curable resin coating liquid A was changed to the acrylic copolymer 4, and the second ultraviolet irradiation was performed under the conditions shown in Table 1 below. A protective layer transfer sheet was produced in the same manner as in Example 8 except that the above was changed.

Comparative Example 4
In Comparative Example 3, a protective layer transfer sheet was prepared in the same manner as in Comparative Example 3, except that the second ultraviolet irradiation was changed to an electron beam and the irradiation was performed under the conditions shown in Table 1.

<Evaluation of protective layer transfer sheet>
Using a thermal transfer sheet provided with a standard dye layer for VDS card printer CP510 on the surface of the image receiving layer of the card base material having the following material composition, an image formed in the order of yellow, magenta, and cyan did.
<Material composition of card base>
・ Polyvinyl chloride compound (degree of polymerization 800) 100 parts (contains 10% additives such as stabilizers)
・ White pigment (titanium oxide) 10 parts ・ Plasticizer (DOP) 0.5 parts

Next, the image receiving layer (image-formed side) of the above-mentioned transfer object is overlapped with the adhesive layer of the protective layer transfer sheet so that the protective layer is placed on the front surface of the transfer object under the following transfer conditions. Formed.
Thermal head: KGT-217-12MPL20 (manufactured by Kyocera Corporation)
-Heating element average resistance: 3195 (Ω)
・ Print density in the main scanning direction: 300 dpi
-Sub-scanning direction printing density: 300 dpi
Applied power: 0.12 (w / dot)
・ One line cycle: 5 (milliseconds)
-Printing start temperature: 40 (° C)
・ Applied pulse: Using a multi-pulse test printer that can vary the number of divided pulses with a pulse length that equally divides a line period into 256 within a line period, and changing the duty ratio of the divided pulses. The card was manufactured by fixing 60%, fixing the number of pulses per line period to 210, performing solid printing, and transferring the protective layer to the entire printing screen.

Under the above transfer conditions, visually evaluate the appearance characteristics of the card after 100 continuous images have been transferred, and check for the presence or absence of burrs on the end face of the card, the presence or absence of burrs on the back edge, Transferability was evaluated by the number of cards with problems. The evaluation criteria were as follows.
◎: The number of problematic cards is 0 to 9 ○: The number of problematic cards is 10 to 19 △: The number of problematic cards is 20 to 29 ×: The number of problematic cards is 30 The evaluation results were as shown in Table 2 below.

Further, the appearance characteristics of the card after the continuous transfer of 100 sheets was visually evaluated according to the following criteria.
○: No problem in appearance Δ: Slight protrusion can be confirmed in appearance ×: Protrusion can be clearly confirmed in appearance The evaluation results are as shown in Table 2 below.

  In addition, the wear resistance test (Taber test) of the protective layer on the card surface is visually observed for each predetermined number of cycles in accordance with ANSI-INCITS 322-2002, 5.9 Surface Abrasion, and the card surface. Those that can visually recognize the image are considered good, and those that are worn out by the surface and difficult to visually recognize or cannot be visually recognized are regarded as defective. ◎ good after 1500 cycles, ◯ good after 1000 cycles, △ good after 1000 cycles but no problems in actual use, bad after 1000 cycles What was there was marked as x. The evaluation results were as shown in Table 2.

  Further, in the protective layer transfer sheet produced as described above, the case where the protective layer transfer sheet was deformed (thermal deformation, deformation due to high-intensity light beam) at the time of transfer was defined as x, and was not deformed based on that. The applicability of the workability was evaluated by assigning “◯” for the product and “Δ” for the slight deformation. The evaluation results were as shown in Table 2 below.

DESCRIPTION OF SYMBOLS 1 Support body 2 Release layer and / or peeling layer 3, 3 'Coating film consisting of actinic ray curable resin 4 Actinic ray curable resin layer 5 Intermediate layer 6 Adhesive layer 10 Protection layer transfer sheet

Claims (22)

A support, and an actinic ray curable resin layer provided on the support via a release layer and / or a release layer, wherein the actinic ray curable resin layer comprises an unsaturated group-containing acrylic copolymer. A method for producing a protective layer transfer sheet comprising an actinic ray curable resin containing a polymer, which is a multistage actinic ray irradiation layer ,
Forming a release layer and / or a release layer on the support;
On the release layer and / or release layer, a coating solution containing an actinic ray curable resin is applied to form a coating film,
In the coating film, at least twice, is irradiated with actinic rays to form active ray curable resin layer, Ri name contains it,
The method, wherein the actinic ray irradiation is performed at least twice in a separate step . The method according to claim 1, wherein the actinic ray curable resin layer comprises fine particles. The method according to claim 2, wherein the fine particles have an average particle diameter of 0.05 to 5 μm. The method according to claim 2 or 3, wherein the fine particles are contained in the actinic ray curable resin layer in a proportion of 0.01 to 30% by mass. The unsaturated group-containing acrylic copolymer has the following general formula (1):

(In the formula, R ₁ and R ₂ each independently represent a hydrogen atom or a methyl group, and R ₃ represents a hydrogen atom, an alkyl group, or an aryl group, but when R ₂ is a methyl group, ₃ represents a hydrogen atom, and L represents a divalent linking group.)
The method as described in any one of Claims 1-4 containing the monomer unit represented by these. The method according to claim 5, wherein the unsaturated group-containing acrylic copolymer contains 0.01 to 50% by mass of the monomer unit of the general formula (1). The method according to claim 5 or 6, wherein the unsaturated group-containing acrylic copolymer has an acid value of 5 to 500 mgKOH / g. The method as described in any one of Claims 1-7 whose mass average molecular weights of the said unsaturated group containing acrylic copolymer are 3000-100000. The method according to claim 1, wherein the actinic ray curable resin comprises 10 to 80% by mass of the unsaturated group-containing acrylic copolymer. The method as described in any one of Claims 1-9 whose thickness of the said actinic-light curable resin layer is 5 micrometers-20 micrometers. The method according to claim 1, further comprising an adhesive layer provided on the actinic ray curable resin layer. The method according to claim 11, further comprising an intermediate layer provided between the actinic ray curable resin layer and the adhesive layer. The method according to any one of claims 1 to 12 , wherein the irradiation with the actinic ray is performed such that the irradiation energy at the second irradiation is higher than the irradiation energy at the first irradiation. The method as described in any one of Claims 1-13 that the actinic ray at the time of the 1st irradiation is an ultraviolet-ray. The method according to claim 14 , wherein the first irradiation is performed with ultraviolet rays having a peak illuminance of 10 to 350 mW / cm ² and an integrated exposure amount of 10 to 200 mj / cm ² . The method according to any one of claims 1 to 15 , wherein the actinic ray of the second irradiation is an ultraviolet ray or an electron beam. The method according to claim 16 , wherein the second irradiation is performed with an ultraviolet ray having an integrated exposure amount of 50 to 500 mj / cm ² . The method according to claim 16 , wherein the second irradiation is performed with an electron beam having an irradiation dose of 50 to 300 kGy. After irradiation of first active light to the coating film, an intermediate layer laminated on the coating film through the intermediate layer, irradiation is performed for the second time to actinic rays, of claims 1 to 18 The method according to any one of the above. After irradiation of first active light to the coating film, an adhesive layer laminated on the coating film via the adhesive layer, irradiation is performed for the second time to actinic rays, of claims 1 to 18 The method according to any one of the above. The method according to claim 19 , wherein after forming the intermediate layer, an adhesive layer is further laminated on the intermediate layer, and a second active light irradiation is performed through the intermediate layer and the adhesive layer. The method according to any one of claims 1 to 21 , wherein after the first irradiation, the second irradiation is performed after at least 2 hours have elapsed.

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