JP2002268523A - Hologram transfer foil - Google Patents

Abstract

PROBLEM TO BE SOLVED: To make clear the preferable range of physical properties to prevent flaw, clouding or vanishing of gloss in a hologram forming layer and to provide a hologram transfer foil as a stable product. SOLUTION: The transfer foil is a surface relief type hologram transfer layer in which a transfer layer of a layered structure having a hologram forming layer and a heat sensitive adhesive layer is laminated on a base film and the farthest layer in the transfer layer from the base film is the heat sensitive adhesive layer. The resin used for the hologram forming layer shows, by the measurement of dynamic viscoelasticity, >=5.0×10<7> Pa dynamic storage elastic modulus in the temperature range from 120 deg.C to 180 deg.C and the maximum point (glass transition point) of tanδ (dynamic loss elastic modulus E"/dynamic storage elastic modulus E') at >=100 deg.C.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a surface relief type which is used for imparting a hologram to various adherends, has good strength, and suppresses white turbidity, loss of gloss and generation of scratches. The present invention relates to a hologram transfer foil.

[0002]

2. Description of the Related Art Conventionally, photocurable resin compositions (paints)
The, for example, to form a photocurable resin layer by coating on a substrate such as a polyester film, and after applying various concave and convex patterns to the photocurable resin layer, exposed to ultraviolet rays or electron beams,
A method has been practiced in which the resin layer is cured, and then a layer having a different refractive index is deposited on the surface of the uneven pattern formed by metal vapor deposition to form a surface relief type hologram transfer foil.

[0003] As a method of providing the above concavo-convex pattern,
For example, when forming a surface relief type hologram, a press stamper (hereinafter simply referred to as a press stamper) prepared from a master hologram having a desired concavo-convex pattern is prepared. Press (emboss) over resin layer
Then, the concavo-convex pattern of the press stamper is transferred to the resin layer, and exposed in this state to cure the resin layer to fix the concavo-convex pattern.

[0004] As a typical layer constitution of the hologram transfer foil obtained by such a production method, a release layer, a hologram forming layer, a reflective thin film layer, and a heat-sensitive adhesive layer are laminated on a base film in this order. Such structures are widely known. In the case of the hologram transfer foil, a transfer layer is formed by a laminated structure including a release layer, a hologram forming layer, a reflective thin film layer, and a heat-sensitive adhesive layer.

[0005]

The hologram transfer foil is:
The transfer layer on the base film is transferred to the transfer object by applying heat pressure when the transfer layer contacts the transfer object. During this thermal transfer, the hologram surface may become cloudy, lose gloss, or have scratches on the surface. However, in the development of the hologram transfer foil so far, it has not been clarified that this is due to the deformation of the hologram forming layer due to heat and pressure,
Therefore, the preferable range of the physical properties of the hologram-forming layer with respect to the hologram transfer foil was not clear. For this reason,
In the case of a hologram using a substance out of the boundary of the preferable range of physical properties, a scratch or white turbidity is generated or a gloss is lost during thermal transfer of the transfer foil, and a hologram image may be disturbed. It was connected.

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a hologram transfer foil capable of clarifying a preferable range of physical properties in order to prevent occurrence of scratches, white turbidity and loss of gloss in a hologram forming layer, and to provide a stable product. And

[0007]

According to the surface relief type hologram transfer foil of the present invention, a transfer layer having a laminated structure having a hologram forming layer and a heat-sensitive adhesive layer is laminated on a substrate film. In the surface relief type hologram transfer foil in which the layer farthest from the base film is the heat-sensitive adhesive layer, the dynamic storage elastic modulus of the resin used in the hologram forming layer is 120 by dynamic viscoelasticity measurement. ° C
From 5.0 × 10 ⁷ Pa to tan δ (dynamic loss modulus E ″) at 100 ° C. or higher.
/ Dynamic storage modulus E ′) (glass transition point).

The reason why the dynamic storage elastic modulus by dynamic viscoelasticity measurement in the present invention is defined in the range of 120 ° C. to 180 ° C. is that the surface relief type hologram transfer foil is thermocompression-bonded to the object in the heat transfer step. In most cases, the transfer is performed at a temperature of 120 ° C. to 180 ° C., and the physical property value in this temperature range affects the properties of the transfer layer to be transferred.

The maximum value of the dynamic storage elastic modulus and the maximum value of tan δ measured by the dynamic viscoelasticity of the resin used in the hologram forming layer is determined by applying heat and pressure to the hologram transfer foil of the present invention using the hologram transfer foil of the above range. The hologram image formed by the transfer becomes a hologram transfer foil capable of stably forming a hologram image in which generation of scratches and cloudiness is suppressed without being thermally deformed in a thermal transfer step.

[0010]

Embodiments of the present invention will be described below in detail. The surface relief type hologram transfer foil of the present invention has a basic layer configuration in which a transfer layer having a laminated structure having a hologram forming layer and a heat-sensitive adhesive layer is laminated on a base film. A release layer may be provided between the substrate film and the hologram-forming layer in order to enhance the releasability of the transfer layer and the substrate film during thermal transfer. Further, when the adhesion between the peeling layer and the hologram forming layer is weak, a layer for improving the adhesion may be provided separately. Further, a reflective thin film layer may be provided between the hologram forming layer and the heat-sensitive adhesive layer.

Substrate Films Substrate films include polyethylene terephthalate (PET) film, polyvinyl chloride (PVC) film, polyvinylidene chloride film, polyethylene film, polypropylene film, polycarbonate film, cellophane film, acetate film, nylon film, Polyvinyl alcohol film, polyamide film, polyamide imide film, ethylene-vinyl alcohol copolymer film, polymethyl methacrylate (PMMA) film, polyether sulfone film, polyether ether ketone (PEEE) film, etc. are exemplified. 5 μm to 200 μm,
Preferably, it is 10 μm to 50 μm.

[0012] The material forming the peeling layer the peeling layer, for example, polymethacrylic acid ester resins, polyvinyl chloride resins, cellulose resins,
One or a mixture of two or more of silicone resin, chlorinated rubber, casein, various surfactants, and metal oxides is used. In particular, the release layer is preferably formed by appropriately selecting its material and the like such that the release force between the base film and the transfer layer is 1 to 5 g / inch (90 ° release). This release layer is preferably formed by ink and formed on the surface of the substrate film by a known method such as coating, and the thickness thereof is preferably in the range of 0.1 to 2 μm in consideration of the release force, foil breakage and the like. .

Hologram forming layer The material for forming the hologram forming layer includes a thermosetting resin,
Various resin materials such as ionizing radiation curable resin can be selected, and the following are exemplified.

Examples of the thermosetting resin include unsaturated polyester resin, acrylic-modified urethane resin, epoxy-modified unsaturated polyester resin, alkyd resin, phenol resin, melamine resin and the like. These resins are used alone or as two or more copolymers. For one or two or more of these resins,
Thermosetting of various isocyanate resins, metal soaps such as cobalt naphthenate and zinc naphthenate, peroxides such as benzoyl peroxide, methyl ethyl ketone peroxide, benzophenone, acetophenone, anthraquinone, naphthoquinone, azobisisobutyronitrile, diphenyl sulfide, etc. And an ultraviolet curing agent.

Examples of the ionizing radiation curable resin include an epoxy-modified acrylic resin, a urethane-modified acrylic resin, an acrylic-modified polyester resin, and the like. Particularly, a urethane-modified acrylic resin represented by the following general formula (1) is preferable.

[0016]

Embedded image

Here, each of the six R ₁ 's independently represents a hydrogen atom or a methyl group, and R ₂ has a carbon number of l.
Represents up to 16 hydrocarbon groups, and Y represents a linear or branched alkylene group. l, m, n, o and p
Where l is 20 to 90 and m is 0,
-80, n is 0-50, o + p is 10-80, p is 0
It is an integer of 40.

The urethane-modified acrylic resin represented by the above formula (1) is preferably, for example, 20 to 90 mol of methyl methacrylate, 0 to 50 mol of methacrylic acid, 10 to 80 mol of 2-hydroxyethyl methacrylate, An acrylic copolymer obtained by copolymerizing 0 to 80 mol of isobornyl methacrylate as Z, wherein methacryloyloxyethyl isocyanate (2-isocyanatoethyl methacrylate) is added to a hydroxyl group present in the copolymer. Is a resin obtained by reacting

It is not necessary that the methacryloyloxyethyl isocyanate has reacted with all the hydroxyl groups present in the copolymer, and at least 10 mol% of the hydroxyl groups of the 2-hydroxyethyl methacrylate units in the copolymer.
As described above, preferably at least 50 mol% should be reacted with methacryloyloxyethyl isocyanate. Instead of or in combination with the above 2-hydroxyethyl methacrylate, N-methylol acrylamide, N-methylol methacrylamide, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl acrylate, 4
Monomers having a hydroxyl group such as -hydroxybutyl methacrylate can also be used.

As described above, by utilizing a hydroxyl group present in a hydroxyl group-containing acrylic resin, a resin composition mainly composed of a urethane-modified acrylic resin in which a large number of methacryloyl groups are introduced in a molecule can be used. When forming a diffraction grating or the like, ionizing radiation such as ultraviolet rays or electron beams can be used as a curing means, and a diffraction grating or the like having excellent flexibility and heat resistance while having a high crosslinking density can be formed. .

The urethane-modified acrylic resin represented by the above formula (1) is dissolved in a solvent capable of dissolving the copolymer, for example, a solvent such as toluene, ketone, cellosolve acetate, or dimethyl sulfoxide. While stirring this solution, methacryloyloxyethyl isocyanate is dropped and reacted, whereby an isocyanate group reacts with a hydroxyl group of the acrylic resin to form a urethane bond, and a methacryloyl group is introduced into the resin through the urethane bond. be able to. The amount of methacryloyloxyethyl isocyanate used at this time is in the range of 0.1 to 5 mol, preferably 0.5 to 3 mol, of isocyanate group per 1 mol of hydroxyl group in a ratio of hydroxyl group to isocyanate group of the acrylic resin. Quantity. When using the methacryloyloxyethyl isocyanate equivalent or more than hydroxyl groups in said resin, -CONH-CH ₂ CH ₂ the methacryloyloxyethyl isocyanate reacts with the carboxyl groups in the resin - resulting ligation of It is possible.

Z in the above formula (1) can be introduced in order to modify the urethane-modified acrylic resin, for example, an aromatic ring such as a phenyl group or a naphthyl group or a heteroaromatic ring such as pyridine. , A monomer having a polymerizable double bond group such as a (meth) acryloyl-modified silicone oil (resin) and a vinyl-modified silicone oil (resin), lauryl (meth)
Monomers having a long-chain alkyl group such as acrylate and stearyl (meth) acrylate; monomers having a silicon-containing group such as γ- (meth) alkoxypropyltrimethoxysilane; 2- (perfluoro-7-methyloctyl)
Ethyl acrylate, heptadecafluorodecyl (meth)
Monomers that impart releasability, such as monomers having a fluorine-containing group such as acrylate, isobornyl (meth) acrylate, cyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate And EO-modified dicyclopentenyl (meth) acrylate and other monomers having a bulky structure, and acryloylmorpholine, vinylpyrrolidone and vinylcaprolactone, and other monomers having a cyclic hydrophilic group.

The above example is based on the general formula (1).
In the case where all R ₁ and R ₂ are methyl groups and X and Y are ethylene groups, the present invention is not limited to these, and each of the five R ₁ is independently a hydrogen atom or methyl. May be a group, and specific examples of R ₂ include, for example,
Methyl group, ethyl group, n- or isopropyl group, n
-, Iso- or tert-butyl group, substituted or unsubstituted phenyl group, substituted or unsubstituted benzyl group and the like. Specific examples of X and Y include ethylene group, propylene group, diethylene group, dipropylene group. And the like.
The thus obtained urethane-modified acrylic resin used in the present invention has a total molecular weight of preferably 10,000 to 200,000, more preferably 20,000 to 100,000 in terms of polystyrene.

The above-mentioned thermosetting or ionizing radiation-curable resin may contain other monofunctional or polyfunctional monomers and oligomers as described below for the purpose of adjusting the cross-linking structure and viscosity. it can.

For example, monofunctional monofunctional (meth) acrylates such as tetrahydrofurfuryl (meth) acrylate, hydroxyethyl (meth) acrylate, vinylpyrrolidone, (meth) acryloyloxyethyl succinate, (meth) acryloyloxyethyl phthalate, etc. In the case of bifunctional or more, when classified by skeleton structure, polyol (meth) acrylate such as epoxy-modified polyol (meth) acrylate, lactone-modified polyol (meth) acrylate, polyester (meth) acrylate, epoxy (meth) acrylate, Urethane (meth) acrylate, other polybutadiene, isocyanuric acid, hydantoin, melamine, phosphoric acid,
Examples include poly (meth) acrylates having skeletons such as imide-based and phosphazene-based, and various monomers, oligomers, and polymers that are curable with ultraviolet light and electron beams can be used.

More specifically, a bifunctional monomer,
As the oligomer, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, neopentyl glycol di (meth)
Acrylate, 1,6-hexanediol di (meth) acrylate, etc., and trifunctional monomers, oligomers and polymers include trimethylolpropane tri (meth) acrylate and pentaerythritol tri (meth) acrylate.
Acrylates, aliphatic tri (meth) acrylates, and the like, and tetrafunctional monomers and oligomers include pentaerythritol tetra (meth) acrylate, ditrimethylolpropanetetra (meth) acrylate, and aliphatic tetra (meth) acrylate. Examples of the monomer or oligomer having five or more functional groups include dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and a (meth) acrylate having a polyester skeleton, a urethane skeleton, and a phosphazene skeleton. Can be

The number of functional groups is not particularly limited, but if the number of functional groups is less than 3, the heat resistance tends to decrease and the dynamic storage elastic modulus measured by dynamic viscoelasticity is 1
5.0 × 10 ⁷ Pa in the range of 20 ° C. to 180 ° C.
And the maximum value of tan δ is 100
It tends to be lower than ° C. Such a dynamic storage modulus and tan δ are applied to the hologram forming layer in the hologram transfer foil.
It is not preferable to use a resin having a value such that a white flaw is formed in a part of the hologram forming layer or the hologram surface tends to be clouded. When the number of functional groups is 20 or more, flexibility tends to decrease.

Any of the above monomers or oligomers can be used in combination, and are used in an amount of about 5 to 90 parts by weight, preferably 10 to 70 parts by weight, per 100 parts by weight of the urethane-modified acrylic resin.

Further, when forming a surface relief type hologram, the material is pressed against a press tamper having irregularities on the surface to form irregularities on the surface of the material. A release agent may be contained in advance so that the resin can be easily peeled off from the press tamper. As the release agent used, a conventionally known release agent,
For example, solid waxes such as polyethylene wax, amide wax, and Teflon (registered trademark) powder, fluorine-based and phosphate-based surfactants, and silicone can be used. Particularly preferred release agents are modified silicones. Specifically, modified silicone oil side chain type, modified silicone oil both terminal type, modified silicone oil one terminal type, modified silicone oil side chain both terminal type, trimethylsiloxysilicic acid (Silicone resin), silicone-grafted acrylic resin, methylphenylsilicone oil and the like.

The modified silicone oil is classified into a reactive silicone oil and a non-reactive silicone oil.
Examples of the reactive silicone oil include amino-modified, epoxy-modified, carboxyl-modified, carbinol-modified, methacryl-modified, mercapto-modified, phenol-modified, one-terminal reactivity, and heterofunctional group-modified. Examples of the non-reactive silicone oil include polyether modification, methylstyryl modification, alkyl modification, higher fatty ester modification, hydrophilic special modification, higher alkoxy modification, higher fatty acid modification, fluorine modification and the like.

Among the above silicone oils, a reactive silicone oil having a group reactive with a film-forming component reacts with and binds to the resin as the resin layer cures. Characteristic performance can be imparted without bleeding out to the surface of the layer. In particular, it is effective for improving the adhesion to the deposition layer in the deposition step.

The hologram-forming material has a cross-linked structure,
An organic metal coupling agent can be added for the purpose of improving the film strength, the adhesion to the deposited layer, and the like. The hologram forming layer to which the organometallic coupling agent is added has an advantage that the dynamic storage modulus, the maximum value of tan δ, and the heat resistance are increased. Examples of the organic metal coupling agent include known silane coupling agents, titanium coupling agents, zirconium coupling agents, and aluminum coupling agents.

Suitable silane coupling agents include, for example, vinyl silane, acrylic silane, epoxy silane, amino silane and the like. More specifically, vinyltrichlorosilane, vinyltris (β-methoxyethoxy) silane, vinyltriethoxysilane, vinyltrimethoxysilane, and the like can be used as the vinylsilane. Further, as the acrylic silane, γ-methacryloxypropyltrimethoxysilane,
γ-methacryloxypropylmethyldimethoxysilane and the like can be mentioned. As epoxysilane, β-
(3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane and the like can be mentioned. Furthermore, as aminosilane, N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane, N-β- (aminoethyl) -γ-aminopropylmethyldimethoxysilane, γ-aminopropyltrimethoxysilane, N- Phenyl-γ-aminopropyltrimethoxysilane and the like can be used.
As other silane coupling agents, γ-mercaptopropyltrimethoxysilane, γ-chloropropylmethyldimethoxysilane, γ-chloropropylmethyldiethoxysilane and the like can be used.

Suitable titanium coupling agents include, for example, titanium alkoxide, titanium chelate and the like. As titanium alkoxide, tetraisopropyl titanate, tetra n-butyl titanate,
Examples of the titanium chelate include titanium acetylacetonate and titanium tetraacetylacetonate.

Suitable zirconium coupling agents include, for example, zirconium alkoxides, zirconium chelates and the like. As the zirconium alkoxide, tetra n-propoxy zirconium,
Tetra-butoxyzirconium, zirconium chelates include zirconium tetraacetylacetonate,
Zirconium dibutoxy bis (acetylacetonate), zirconium tributoxyethyl acetoacetate, zirconium butoxyacetylacetonate bis (ethyl acetoacetate) and the like.

Suitable aluminum coupling agents include, for example, aluminum alcoholate, aluminum chelate, cyclic aluminum oligomer and the like. More specifically, as the aluminum alcoholate, aluminum isopropylate, monosec
-Butoxyaluminum diisopropylate, aluminum sec-butyrate, aluminum ethylate, and aluminum chelate include ethyl acetoacetate aluminum diisopropylate, aluminum tris (ethyl acetoacetate), alkyl acetoacetate aluminum diisopropylate, and aluminum monoacetylacetonate Bis (ethylacetoacetate), aluminum tris (acetylacetonate) and the like can be mentioned. Such an organic metal coupling agent is preferably used in a range of 0.1 to 10 parts by weight per 100 parts by weight of the urethane-modified acrylic resin.

When the resin used for the hologram-forming layer is cured by ultraviolet rays, a photosensitizer is added to the composition. As the photosensitizer, various photosensitizers used in conventional ultraviolet curable resins, for example, benzoin,
Benzoin compounds such as benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, α-methylbenzoin, α-phenylbenzoin, anthraquinone compounds such as anthraquinone and methylanthraquinone, phenylketone compounds such as benzyldiacetylacetophenone and benzophenone, diphenyldis Sulfide compounds such as sulfide and tetramethylthiuram sulfide; and α-chloromethylnaphthalene, anthracene, and halogenated hydrocarbons such as hexachlorobutadiene and pentachlorobutadiene. Such a photosensitizer is the urethane-modified acrylic resin 1
It is preferably used in the range of about 0.5 to 2.0 parts by weight per 00 parts by weight.

In the hologram-forming layer, in addition to the above components, phenols such as hydroquinone, t-butylhydroquinone, catechol and hydroquinone monomethyl ether, quinones such as benzoquinone and diphenylbenzoquinone, phenothiazines and coppers. Addition of a polymerization inhibitor improves storage stability. Further, if necessary,
Various assistants such as an accelerator, a viscosity modifier, a surfactant, and an antifoaming agent may be blended. Further, a polymer such as styrene / butadiene rubber can be blended.

The maximum value of the dynamic storage elastic modulus (E ') and the maximum value of tan δ by dynamic viscoelasticity measurement of the hologram forming layer can be measured by the following methods. (Dynamic viscoelasticity measuring method)-Measuring equipment: Solid viscoelasticity analyzer RSA-II (trade name, manufactured by Rhemetrics)-Measuring mode: Film tension method-Measuring temperature: -50C to 300C-Measurement heating rate: 5 ° C / min ^-1 · Measurement frequency: 6.28 rad / s · Measurement sample properties: As a measurement sample, a hologram-forming material intended for measurement is applied on a base film at a specific thickness, and the material is thermoset. When the resin is a curable or ionizing radiation curable resin, it is cured by a predetermined method, and is peeled off from the substrate film to obtain a test piece having a width of 5 to 10 mm and a length of 20 to 50 mm. In addition, when the surface of the base film is subjected to the release treatment during the formation of the film, it is easy to peel it off later. Measurement method: The prepared sample is set on a jig for tensile measurement, and the temperature dependence of the dynamic viscoelasticity of the sample is measured. From the data, the value of the dynamic storage modulus E ′ in the temperature range from 120 ° C. to 180 ° C. is determined. Further, the dynamic loss elastic modulus E ″ / dynamic storage elastic modulus E ′ = tan δ is determined, and the temperature at the maximum value is determined.

[0040] As the reflective layer reflecting layer, the use of thin metal film which reflects light becomes opaque type hologram, becomes a used when the transparent type thin film with a refractive index difference between the hologram forming layer of a transparent material, both the Can be used for invention. The reflection layer can be formed by a known method such as sublimation, vacuum deposition, sputtering, reactive sputtering, ion plating, and electroplating.

As a metal thin film for forming an opaque hologram, for example, Cr, Ti, Fe, Co, N
i, Cu, Ag, Au, Ge, Al, Mg, Sb, P
b, Pd, Cd, Bi, Sn, Se, In, Ga, Rb
Is a thin film formed by using a metal such as and the like, an oxide and a nitride thereof alone or in combination of two or more kinds. Among the above metal thin films, Al, Cr, Ni, Ag, Au and the like are particularly preferable, and the film thickness is 1 to 10,000 nm, preferably 2 to 10,000 nm.
The range is from 0 to 200 nm.

As the thin film for forming the transparent hologram, any material can be used as long as it is a light-transmitting material capable of exhibiting the hologram effect. For example, there is a transparent material having a different refractive index from the resin of the hologram forming layer (photocurable resin layer). The refractive index in this case may be higher or lower than the refractive index of the resin of the hologram forming layer, but the difference in the refractive index is preferably 0.1 or more, more preferably 0.5 or more.
And 1.0 or more is optimal. In addition to the above, there is a metallic reflective film having a thickness of 20 nm or less. As the transparent type reflection layer preferably used, an acid value titanium (Ti
O ₂ ), zinc sulfide (ZnS), and Cu / Al composite metal oxide.

Heat-sensitive adhesive layer The heat-sensitive adhesive layer includes ethylene-vinyl acetate copolymer resin, polyamide resin, polyester resin, polyethylene resin, ethylene-isobutyl acrylate copolymer resin,
Butyral resin, polyvinyl acetate and its copolymer resin, cellulose resin, polymethyl methacrylate resin, polyvinyl ether resin, polyurethane resin, polycarbonate resin, polypropylene resin, epoxy resin, phenol resin, SBS, SIS, SEBS, SE
A thermoplastic resin such as PS is included.

In the case of performing transfer using a hologram transfer foil of the transfer present invention, the hologram transfer foil of the present invention on the surface of the transfer receiving material to be applied to the hologram, as the heat-sensitive adhesive layer is in contact with the transfer side The transfer foil is heated and pressed with a pressure plate or the like on the transfer foil at the portion where the hologram is to be superimposed, and the desired portion of the heat-sensitive adhesive layer is melt-bonded. Then, only the desired portion of the transfer layer is transferred, and a hologram can be provided on the surface of the transfer object.

[0045]

EXAMPLES Example 1 i) Production of Resin A In a 2 liter four-necked flask equipped with a condenser, a dropping funnel and a thermometer, 40 g of toluene and 40 g of MEK were charged together with an azo-based initiator, and 24.6 g of HEMA was added. , MM
A73.7 g, dicyclopentenyloxyethyl methacrylate 24.6 g, toluene 20 g, and MEK20
The mixture was allowed to react at a temperature of 100 to 110 ° C. for 8 hours while dropping the mixed solution of g through a dropping funnel over about 2 hours, and then cooled to room temperature.

To this were added 27.8 g of 2-isocyanatoethyl methacrylate, 20 g of toluene and 20 g of MEK.
And an addition reaction was carried out using dibutyltin laurate as a catalyst. 2200 by IR analysis of the reaction product.
The disappearance of the absorption peak at cm-1 was confirmed, and the reaction was terminated.
The solid content of the obtained resin solution was 41.0%, the molecular weight was 30,000 in terms of polystyrene, and the amount of C = C bond introduced was 13.
It was 0 mol%. The obtained resin is referred to as a resin A. The resin A is a resin represented by the following general formula (2) in which dicyclopentenyloxyethyl methacrylate is introduced into Z in the general formula (1).

[0047]

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Ii) Preparation of photosensitive resin composition for hologram formation A composition having the following compounding ratio was prepared by adding methyl ethyl ketone (ME
The mixture was diluted with K) to adjust the solid content of the composition to 50%, and a photosensitive resin for forming the hologram-forming layer of Example 1 was prepared. Resin A (solid content basis) 100 parts Silicone: trimethylsiloxysilicate-containing methylpolysiloxane (KF-7 312: trade name, manufactured by Shin-Etsu Chemical Co., Ltd.) 1 part Dipentaerythritol monohydroxypentaacrylate (SR-399: trade name) Product name, Sartomer, pentafunctional monomer 70 parts Photosensitizer (Irgacure 907: trade name, manufactured by Ciba Specialty Chemicals) 5 parts iii) Production of laminate composed of release layer / PET film 25 μm polyethylene terephthalate film (Lumirror) T60: trade name, manufactured by Toray Industries, Inc.) 20m / mi
n. A varnish is applied with a gravure coat at a speed of 10 μm.
After drying at 0 ° C. to evaporate the solvent and form a release layer,
A film having a dry film thickness of 1 g / m ² and a layer structure of release layer / PET was obtained.

Iv) Production of photosensitive film for duplication On the release layer of the film having the layer structure of PET / release layer obtained in the above step, the resin A obtained in the above step is coated with a roll coater, After drying at 100 ° C. to evaporate the solvent, a photosensitive film for duplication having a dry film thickness of 2 g / m ² was obtained. All of the obtained films were not sticky at room temperature and could be stored in a wound state.

V) Dynamic storage elastic modulus (E ') and tan δ by dynamic viscoelasticity measurement The above-mentioned photocurable resin composition alone was formed into a film and exposed to ultraviolet rays at a total exposure of 600 mJ / cm ² . .
FIG. 1 is a graph showing the results of dynamic storage elastic modulus (E ′) and tan δ measured by dynamic viscoelasticity of the obtained film having a thickness of 80 μm. According to FIG. 1, the lowest part of the dynamic storage modulus (E ′) in the range of 120 ° C. to 180 ° C. is 1.03 × 10 ⁸ Pa, and the maximum value of tan δ is 124.3 ° C. Was.

Comparative Example 1 The same production method as in Example 1 was performed except that 50 parts of a pentafunctional monomer was used and 20 parts of a bifunctional urethane acrylate (UV3000B: trade name, manufactured by Nippon Synthetic Chemical Co., Ltd.) was added. The hologram-forming photosensitive resin composition of Comparative Example 1 was obtained.

For the resin of Comparative Example 1, the dynamic storage modulus (E ') and tan δ were measured in the same manner as in Example 1. The obtained result is shown as a graph in FIG. FIG.
According to this, the lowest part of the dynamic storage modulus (E ′) in the range of 120 ° C. to 180 ° C. is 3.37 × 10 ^7.
Pa, and the maximum value of tan δ was 99.8 ° C.

In Comparative Example 1, the dynamic storage modulus (E ') and t
The reason for the decrease in the maximum value of an δ is that the added urethane acrylate (UV3000B: trade name, manufactured by Nippon Synthetic Chemical Co., Ltd.) is bifunctional, so that the cured coating film has a low crosslinking density and dynamic storage elasticity. Rate (E ′) and tan δ
It is considered that the maximum value of was lowered.

Example 2 i) Production of Resin B A 2-liter four-necked flask equipped with a condenser, a dropping funnel and a thermometer was charged with 40 g of toluene and 40 g of methyl ethyl ketone (MEK) together with an azo-based initiator. 2
-Hydroxyethyl methacrylate (HEMA) 20.
8 g, methyl methacrylate (MMA) 39.0 g, isobornyl methacrylate 45.0 g, toluene 20
g and 20 g of MEK were allowed to react at a temperature of 100 to 110 ° C. for 8 hours while being dropped through a dropping funnel over about 2 hours, and then cooled to room temperature.

In addition, 2-isocyanate ethyl methacrylate (manufactured by Showa Denko, Karenz MOI: trade name)
A mixed solution of 3.4 g, 20 g of toluene and 20 g of MEK was added, and an addition reaction was carried out using dibutyltin laurate as a catalyst. The disappearance of the absorption peak at 2200 cm-1 was confirmed by IR analysis of the reaction product, and the reaction was terminated. The solid content of the obtained resin solution was 38.2%, the molecular weight was 30,000 in terms of polystyrene, and the amount of C ＝ C bond introduced was 12.5 mol%. The obtained resin is referred to as a resin B. The resin B is a resin represented by the following general formula (3) in which isobornyl methacrylate is introduced into Z in the general formula (1).

[0056]

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Ii) Preparation of photosensitive resin composition for hologram formation A composition having the following compounding ratio was prepared by adding methyl ethyl ketone (ME
By diluting with K), the solid content of the composition was adjusted to 50%, and a photosensitive tree composition for forming a hologram-forming layer of Example 2 was prepared. Resin B (based on solid content) 100 parts Silicone oil: Amino-modified reactive silicone oil (side chain type) (KF-860: trade name, manufactured by Shin-Etsu Chemical Co., Ltd.) 1 part Dipentaerythritol monohydroxypentaacrylate (SR -399: Trade name, manufactured by Sartomer, pentafunctional monomer) 40 parts Photosensitizer (Irgacure 907: trade name: manufactured by Ciba Specialty Chemicals) 5 parts iii) Production of release layer / PET film laminate A laminate comprising a release layer / PET film was produced in the same manner as in the method for producing a release layer / PET film laminate of No. 1.

[0058] iv) except for using the prepared resin B of the duplication photosensitive film performs a manufacturing method of Example 1 the same duplication photosensitivity and film, this embodiment of the dry film thickness 2 g / m ² 2 Was obtained. All of the obtained films were not sticky at room temperature and could be stored in a wound state.

V) Dynamic storage elastic modulus (E ') and tan δ by dynamic viscoelasticity measurement A film of the above photocurable resin composition alone was exposed to ultraviolet light at a total exposure of 600 mJ / cm ² . .
FIG. 3 is a graph showing the results of dynamic storage elastic modulus (E ′) and tan δ measured by dynamic viscoelasticity for the obtained film having a thickness of 80 μm. According to FIG. 3, the lowest part of the dynamic storage modulus (E ′) in the range of 120 ° C. to 180 ° C. is 9.89 × 10 ⁷ Pa, and the maximum value of tan δ is 104.1 ° C. Was.

Comparative Example 2 Resin B in Example 2
Was carried out in the same manner as in Example 2 except that the resin A was replaced with the resin A, thereby obtaining a hologram-forming photosensitive resin composition of Comparative Example 2.

For the resin of Comparative Example 2, the dynamic storage modulus (E ') and tan δ were measured in the same manner as in Example 1. The obtained result is shown as a graph in FIG. FIG.
According to this, the lowest part of the dynamic storage modulus (E ′) in the range of 120 ° C. to 180 ° C. is 4.70 × 10 ^7.
Pa, and the maximum value of tan δ was 121.3 ° C. The reason why the maximum values of the dynamic storage modulus (E ′) and the tan δ were lower in Comparative Example 2 than in Examples 1 and 2 is that resin A is more bulky than resin B in example 2. It is considered that the amount of the high isobornyl group was small and that the ratio of the resin A used in Comparative Example 2 was lower than that in Example 1.

Example 3 i) Production of Resin C In a 2 liter four-necked flask equipped with a condenser, a dropping funnel and a thermometer, 40 g of toluene and 40 g of MEK were charged together with an azo-based initiator, and 22.4 g of HEMA was added. MM
A mixture of 70.0 g of A, 20 g of toluene, and 20 g of MEK was allowed to react at a temperature of 100 to 110 ° C. for 8 hours while being dropped through a dropping funnel over about 2 hours, and then cooled to room temperature.

Then, 27.8 g of 2-isocyanatoethyl methacrylate, 20 g of toluene and 26 g of MEK were added.
And an addition reaction was carried out using dibutyltin laurate as a catalyst. 2200 by IR analysis of the reaction product.
The disappearance of the absorption peak at cm-1 was confirmed, and the reaction was terminated.
The solid content of the obtained resin solution is 41.0%, and the viscosity is 130.
mPa (30 ° C.), molecular weight is 250 in terms of polystyrene.
00, the amount of C = C bond introduced was 13.8 mol%. The obtained resin is called a resin C, and the resin C is a resin represented by the following general formula (4) when there is no Z in the general formula (1).

[0064]

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Ii) Preparation of Photosensitive Resin Composition for Hologram Formation A composition having the following compounding ratio was prepared by adding methyl ethyl ketone (ME
The solid content of the composition was adjusted to 50% by dilution with K) to prepare a photosensitive tree composition for forming a hologram-forming layer of Example 3. Resin C (solid content basis) 100 parts Silicone oil: Amino-modified reactive silicone oil (one-end type) (KF-8012: trade name, manufactured by Shin-Etsu Chemical Co., Ltd.) 1 part Dipentaerythritol monohydroxypentaacrylate (SR -399: Trade name, manufactured by Sartomer, pentafunctional monomer 40 parts Aluminum coupling agent (S-75P: trade name, manufactured by Kawaken Fine Chemical) 5 parts Photosensitizer (Irgacure 907: trade name, Ciba Special Chemicals) 5 parts) iii) Production of laminate comprising release layer / PET film In the same manner as in the method for producing a laminate comprising release layer / PET film of Example 1, lamination comprising release layer / PET film. Body manufactured.

Iv) Production of photosensitive film for duplication The same method for producing a photosensitive film for duplication was carried out as in Example 1 except that resin C was used, and this Example 3 having a dry film thickness of 2 g / m ² was used. Was obtained. All of the obtained films were not sticky at room temperature and could be stored in a wound state.

V) Dynamic storage elastic modulus (E ') and tan δ by dynamic viscoelasticity measurement A film formed of only the above photocurable resin composition was exposed to ultraviolet rays at a total exposure of 600 mJ / cm ² . .
FIG. 5 is a graph showing the results of dynamic storage elastic modulus (E ′) and tan δ measured by dynamic viscoelasticity for the obtained film having a thickness of 80 μm. According to FIG. 5, the lowest part of the dynamic storage modulus (E ′) in the range of 120 ° C. to 180 ° C. is 5.62 × 10 ⁷ Pa, and the maximum value of tan δ is 106.0 ° C. Was.

Comparative Example 3 A hologram-forming photosensitive resin composition of Comparative Example 3 was obtained in the same manner as in Example 3 except that the aluminum coupling agent was not added. Was.

The dynamic storage modulus (E ') and tan δ of the resin of Comparative Example 3 were measured in the same manner as in Example 1. The results obtained are shown as a graph in FIG. FIG.
According to this, the lowest part of the dynamic storage modulus (E ′) in the range of 120 ° C. to 180 ° C. is 2.98 × 10 ^7.
Pa, and the maximum value of tan δ was 95.4 ° C.
The reason why the maximum values of the dynamic storage modulus (E ′) and tan δ in Comparative Example 3 were low is that the crosslinking density was low because the aluminum coupling agent was not added, and the dynamic storage modulus (E ′) was low. It is considered that the maximum values of tan δ and tan δ became low.

Example 4 i) Production of Resin D A 2-liter four-necked flask equipped with a cooler, a dropping funnel and a thermometer was charged with 40 g of toluene and 40 g of MEK together with an azo-based initiator. MM
A36.0 g, isobonyl methacrylate 109.6
g, 20 g of toluene, and 20 g of MEK through a dropping funnel, while dropping the mixture over about 2 hours.
After reacting at a temperature of 110 ° C. for 8 hours, it was cooled to room temperature.

To this were added 28.8 g of 2-isocyanateethyl methacrylate, 20 g of toluene and MEK20.
g of the mixed solution was added to carry out an addition reaction using dibutyltin laurate as a catalyst. 220 analysis of the reaction product by IR analysis.
The disappearance of the absorption peak at 0 cm-1 was confirmed, and the reaction was terminated. The obtained resin solution has a solid content of 37.0% and a viscosity of 1
30 mPa (30 ° C.), molecular weight of 6 in terms of polystyrene
0000, the amount of C = C bond introduced was 12.8 mol%. The obtained resin is referred to as a resin D. The resin D is a resin represented by the following general formula (5) in which isobornyl methacrylate is introduced into Z in the general formula (1).

[0072]

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Ii) Preparation of photosensitive resin composition for hologram formation A composition having the following compounding ratio was prepared by adding methyl ethyl ketone (ME
By diluting with K), the solid content of the composition was adjusted to 50%, and a photosensitive tree composition for forming a hologram-forming layer of Example 4 was prepared. Resin D (solid content basis) 100 parts Silicone oil: Trimethylsiloxysilicate-containing methylpolysiloxane (KF-7312: trade name, manufactured by Shin-Etsu Chemical Co., Ltd.) 1 part Dipentaerythritol monohydroxypentaacrylate (SR-399: Trade name, Sartomer, pentafunctional monomer) 40 parts Aluminum coupling agent (ALCH-TR: trade name, manufactured by Kawaken Fine Chemical) 5 parts Photosensitizer (Irgacure 907: trade name, manufactured by Ciba Specialty Chemicals) 5 parts iii) Production of release layer / PET film laminate Production of release layer / PET film laminate by the same method as in the production method of release layer / PET film laminate of Example 1 above. did.

Iv) Production of photosensitive film for duplication The same method for producing a photosensitive film for duplication was carried out as in Example 1 except that resin D was used, and this Example 4 was dried at a dry film thickness of 2 g / m ^2. Was obtained. All of the obtained films were not sticky at room temperature and could be stored in a wound state.

V) Dynamic storage elastic modulus (E ') and tan δ by dynamic viscoelasticity measurement A film formed of only the above-mentioned photocurable resin composition was exposed to ultraviolet rays at a total exposure of 600 mJ / cm ² . .
FIG. 7 is a graph showing the results of dynamic storage elastic modulus (E ′) and tan δ obtained by dynamic viscoelasticity measurement for the obtained film having a thickness of 80 μm. According to FIG. 7, the lowest part of the dynamic storage modulus (E ′) in the range of 120 ° C. to 180 ° C. is 6.06 × 10 ⁷ Pa, and the maximum value of tan δ is 142.5 ° C. Was. In Example 4, the dynamic storage modulus was increased by increasing the molecular weight of the polymer itself and increasing the proportion of bulky groups, and tan δ
It is considered that the maximum value of was able to be increased.

Example 5 Copy of hologram The hologram was copied using the respective photosensitive films for copying of Examples 1 to 4 as follows. The hologram duplication was performed by the continuous duplication apparatus shown in FIG. 1 described in JP-A-61-156273. The emboss roller on the surface of which the hologram master of the continuous copying machine is formed,
A press stamper continuously created from a master hologram created using laser light is installed. In addition,
A duplicate hologram prepared from a master hologram on a resin plate and attached to a cylinder can also be used. Each of the photosensitive films for duplication prepared above was set on the paper feed side, and heated and pressed at 150 ° C. to form a fine uneven pattern. Subsequently, ultraviolet light generated from a mercury lamp was irradiated to perform photocuring. Subsequently, an aluminum layer was deposited thereon by a vacuum deposition method to form a reflection type surface relief hologram. On this surface, a heat-sensitive adhesive (HS
-32 mat: trade name, Showa Ink Industries Co., Ltd.) coated with a gravure coat, dried at 100 ° C., and the solvent is dispersed to form a heat-sensitive adhesive layer having a dry film thickness of 3 g / m ^2. did.

From the base film side of the obtained transfer foil, 16
Heat and press with a mold set at 0 ° C, 170 ° C, and 180 ° C to transfer to a vinyl chloride card, and confirm that the transferred hologram is in close contact with the vinyl chloride card by a cross-cut peeling test with an adhesive tape. did. The results are shown in Table 1 below. A hologram image that was satisfactorily transferred without any disturbance was evaluated as ○, a hologram image having a white flaw in a part thereof was evaluated as x, and a hologram image having cloudy hologram surface was evaluated as XX.

Comparative Example 4 A hologram was duplicated under the same conditions as in Example 5 using the photosensitive films for duplication of Comparative Examples 1 to 3. The results are shown in Table 1 below. Evaluation criteria for the adhesive tape cross-cut peeling test are the same as those in Example 5.

[0079]

[Table 1]

[0080]

According to the present invention, it is possible to clarify the preferable range of the physical properties in which the occurrence of scratches and white turbidity and the loss of gloss of the hologram forming layer in the hologram transfer foil are suppressed, and these disadvantages are caused during thermal transfer. Can provide a stable surface relief type hologram transfer foil in which the hologram transfer foil is suppressed.

[Brief description of the drawings]

FIG. 1 is a graph showing the results of dynamic storage elastic modulus (E ′) and tan δ measured by dynamic viscoelasticity for a film obtained by molding only the photocurable resin composition of Example 1.

FIG. 2 is a graph showing the results of dynamic storage elastic modulus (E ′) and tan δ measured by dynamic viscoelasticity for a film obtained by film-forming only the photocurable resin composition of Comparative Example 1.

FIG. 3 is a graph showing the results of dynamic storage elastic modulus (E ′) and tan δ measured by dynamic viscoelasticity for a film obtained by film-forming only the photocurable resin composition of Example 2.

FIG. 4 is a graph showing the results of dynamic storage elastic modulus (E ′) and tan δ measured by dynamic viscoelasticity for a film obtained by forming a film of only the photocurable resin composition of Comparative Example 2.

FIG. 5 is a graph showing the results of dynamic storage elastic modulus (E ′) and tan δ measured by dynamic viscoelasticity for a film obtained by film-forming only the photocurable resin composition of Example 3.

FIG. 6 is a graph showing the results of dynamic storage elastic modulus (E ′) and tan δ measured by dynamic viscoelasticity for a film obtained by molding only the photocurable resin composition of Comparative Example 3.

FIG. 7 is a graph showing the results of dynamic storage elastic modulus (E ′) and tan δ measured by dynamic viscoelasticity of a film obtained by molding only the photocurable resin composition of Example 4.

Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (reference) C08L 83/04 C08L 83/04 101/12 101/12 G02B 1/04 G02B 1/04 G03H 1/20 G03H 1/20 F-term (reference) 2K008 AA11 EE01 EE04 FF12 FF13 FF14 GG05 4F100 AH08B AK01B AK25B AK41B AK42 AL05B AL06B AR00B AR00C AR00D AT00A BA03 BA04 BA07 BA10A BA10C CB00C EH46 EJ05B EJ54 GB90 JB13B JB14B JK07 JK07B JK14 JL12C JL14D JN17B JN21 JN28 JN30B YY00B 4J002 AA02W BG07X CC03W CC10W CC18W CF01W CF21W CF27X CP03Y EX016 EX036 EX046 EZ006 FD16Y FD206 GP00

Claims (8)

[Claims] A transfer layer having a laminated structure having a hologram forming layer and a heat-sensitive adhesive layer is laminated on a base film, and a layer of the transfer layer farthest from the base film is heat-sensitive adhesive. In the surface relief type hologram transfer foil as the agent layer, the dynamic storage elastic modulus of the resin composition used in the hologram forming layer measured by dynamic viscoelasticity is 5.0 × 10 5 in the range of 120 ° C. to 180 ° C. ⁷ Pa or more and 100
A hologram transfer foil having a maximum value of tan δ (dynamic loss elastic modulus E ″ / dynamic storage elastic modulus E ′) of not less than ° C. 2. The hologram transfer foil according to claim 1, wherein a layer closest to the base film in the transfer layer is a release layer. 3. The hologram transfer foil according to claim 1, wherein the resin composition constituting the hologram-forming layer includes a resin selected from a thermosetting resin and an ionizing radiation-curable resin. 4. The ionizing radiation-curable resin contained in the resin composition constituting the hologram-forming layer is one or two selected from an epoxy-modified acrylic resin, a urethane-modified acrylic resin, and an acrylic-modified polyester resin. The hologram transfer foil according to claim 3, which is as described above. 5. The ionizing radiation-curable resin contained in the resin composition constituting the hologram-forming layer is a urethane-modified acrylic resin represented by the following general formula.
The hologram transfer foil according to the above. Embedded image (Wherein, six R _{1 s} each independently represent a hydrogen atom or a methyl group, R ₂ represents a hydrocarbon group having 1 to 16 carbon atoms, and Y represents a linear or branched chain. And the total of l, m, n, o and p is 10
When 0, 1 is an integer of 20 to 90, m is an integer of 0 to 80, n is an integer of 0 to 50, o + p is an integer of 10 to 80, and p is an integer of 0 to 40. ) 6. The resin composition constituting the hologram-forming layer has a crosslink density increased by blending and polymerizing a polyfunctional monomer or oligomer having 3 to 20 functional groups. 3. The hologram transfer foil according to 3. 7. The hologram transfer foil according to claim 3, wherein the resin composition constituting the hologram-forming layer contains a release component. 8. The hologram transfer foil according to claim 3, wherein the resin composition constituting the hologram forming layer contains an organic metal coupling agent.