JP3357014B2 - Photocurable resin composition and method for forming uneven pattern - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photocurable resin composition and a method for forming a concavo-convex pattern, and more particularly to a method for forming a urethane-modified acrylic resin capable of forming a film having both heat resistance and flexibility. The present invention relates to a photocurable resin composition serving as a discharge forming component, and a method for forming a concavo-convex pattern such as a diffraction grating or a relief hologram.

[0002]

2. Description of the Related Art Conventionally, photocurable resin compositions (paints) have been
For example, a photocurable resin layer is formed by coating on a base material such as a polyester film, and after applying various concavo-convex patterns to the photocurable resin layer, the resin layer is exposed to ultraviolet rays or electron beams. There is a method in which the layer is cured, and then a layer having a different refractive index is deposited on the surface of the concavo-convex pattern formed by metal deposition to form a diffraction grating or a relief hologram.

[0003] As a method of providing the above concavo-convex pattern,
For example, when forming a relief 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, and the press stamper is made of the photocurable resin. The layer is pressed (embossed) on top of the layer, and the concavo-convex pattern of the press stamper is transferred to the resin layer. In this state, the resin layer is exposed and cured to fix the concavo-convex pattern. When a large number of relief holograms are formed in this manner, a large number of embossing processes are performed by one press stamper.

[0004]

In many cases, the conventional photocurable paints described above are in a liquid state, so that the storage stability of the paint is inferior and the quality stability of the uneven pattern of a thin hologram or the like is uneasy. is there. In addition, when a conventional photocurable paint is used, since many additives are blended in the paint, if the embossing process is repeated many times, the components in the paint adhere to the press stamper. However, the fine concavo-convex pattern of the press stamper is impaired, and similarly, the quality of the obtained hologram and the like becomes unstable.

[0005] Furthermore, diffraction gratings and relief holograms are conventionally used for decoration of various cards and securities, and for the purpose of preventing forgery. With the expansion of their applications, more excellent strength, heat resistance, scratch resistance, Water resistance, chemical resistance, and adhesion to a substrate are required, and the adherence to an object to be bent or stretchable is required. In particular, in the case of a diffraction grating or relief hologram made of a conventional photocurable paint, the resin used loses flexibility due to photocuring, and as a result, the diffraction grating or relief hologram is bent or stretched by the adherend. Function was lost.

In order to solve these problems, there have been proposed material systems disclosed in Japanese Patent Application Laid-Open No. 61-156273 and Japanese Patent Publication No. 5-54502. However,
The reactive resin described in JP-A-61-156273 is a resin having a hydroxyethyl methacrylate unit in the main chain, which is further added with hydroxyethyl methacrylate via diisocyanate to form a double bond with the resin. Because of the introduction method, it has been difficult to introduce a double bond as designed, and there has been a problem that the resin is easily gelled by being affected by a small amount of water in the system. Further, the reactive resin described in Japanese Patent Publication No. 5-54502 has a melamine skeleton, and thus is slightly inferior in water resistance.
When there is a methylol group, there is a problem that formaldehyde is generated by hydrolysis.

[0007] Accordingly, an object of the present invention is to provide excellent strength, heat resistance and scratch resistance without using a material system as disclosed in the above-mentioned JP-A-61-156273 and JP-B-5-54502. Which can form a diffraction grating, relief hologram, etc., which can form a film having water resistance, water resistance, chemical resistance, and adhesion to a substrate, and also has the ability to follow the flexibility and expansion and contraction of an adherend. An object of the present invention is to provide a curable dendritic composition and a method for forming an uneven pattern.

[0008]

The above object is achieved by the present invention described below. That is, the photocurable resin composition of the present invention is a urethane-modified acrylic resin represented by the following structural formula (1).

[0009]

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(Wherein five R _{1 s} each independently represent a hydrogen atom or a methyl group, R ₂ represents a C ₁ -C ₁₆ hydrocarbon group, and X and Y represent a linear or branched chain. Where l is from 20 to 90, m is from 0 to 50, and n is 10 when the total of l, m, n and o is 100.
-80 and o are integers of 0-20. A release agent; and a polyfunctional monomer having a structure containing an alkylene oxide chain or a skeleton represented by the following formula (2):

[0011]

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(Wherein R ₁ is a linear or branched alkylene group having 2 to 8 carbon atoms, and n is an integer of 20 or less, preferably 5 or less). Features.

The photocurable resin composition of the present invention contains the above components to form a film having excellent strength, heat resistance, scratch resistance, water resistance, chemical resistance, and adhesion to a substrate. It is possible to form a diffraction grating, a relief hologram, or the like, which is possible and has a followability to the flexibility and expansion and contraction of the adherend.

The photocurable resin composition of the present invention contains a polyfunctional monomer containing a skeleton represented by the structural formula of the above formula (2) or an alkylene oxide chain in the structure. Has a relatively long chain, that is, contains a long spacer component between the functional groups, and easily forms a network with the urethane-modified acrylic resin represented by the structural formula of the formula (1). The reactivity increases. A film formed using such a photocurable resin composition has a high crosslink density, so that a strong and stable film is formed, so that the diffraction grating or relief hologram to which the film is applied is stable. Becomes

[0015]

Next, the photocurable resin composition of the present invention and the method of forming a concavo-convex pattern will be described in more detail with reference to preferred embodiments.

Urethane-Modified Acrylic Resin The photocurable resin composition of the present invention contains a urethane-modified acrylic resin as an essential component. A preferred example of the urethane-modified acrylic resin is an acrylic copolymer obtained by copolymerizing 20 to 90 mol of methyl methacrylate, 0 to 50 mol of methacrylic acid, and 10 to 80 mol of 2-hydroxyethyl methacrylate. And a resin obtained by reacting methacryloyloxyethyl isocyanate (2-isocyanatoethyl methacrylate) with a hydroxyl group present in the copolymer.

In the urethane-modified acrylic resin exemplified above, it is not necessary for methacryloyloxyethyl isocyanate to react with all the hydroxyl groups present in the copolymer, and 2-hydroxyethyl methacrylate in the copolymer may be used. It is sufficient that at least 10 mol% or more, preferably 50 mol% or more of the hydroxyl groups of the unit have reacted with methacryloyloxyethyl isocyanate. 2 above
N-methylolacrylamide, N-methylolmethacrylamide, 2-hydroxyethylacrylate, instead of or in combination with -hydroxyethyl methacrylate,
Monomers having a hydroxyl group such as 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl acrylate, and 4-hydroxybutyl methacrylate can also be used.

As described above, a resin composition containing, as a main component, a urethane-modified acrylic resin having a large number of methacryloyl groups introduced into the molecule by utilizing the hydroxyl groups present in the hydroxyl-containing acrylic resin is used. Thereby, for example, when forming a diffraction grating or the like, ionizing radiation such as ultraviolet rays or an electron beam can be used as a curing means, and a diffraction grating or the like excellent in flexibility and heat resistance while having a high crosslinking density is formed. can do.

Method for producing urethane-modified acrylic resin:
Solvent capable of dissolving the copolymer, for example, toluene,
By dissolving in a solvent such as ketone, cellosolve acetate, dimethyl sulfoxide and the like, and stirring and stirring this solution, methacryloyloxyethyl isocyanate is dropped and reacted, whereby the isocyanate group reacts with the hydroxyl group of the acrylic resin to form a urethane bond. And a methacryloyl group can be introduced into the resin via the urethane bond. 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 methacryloyloxyethyl isocyanate is used in an amount equal to or more than the hydroxyl group in the resin, the methacryloyloxyethyl isocyanate also reacts with a carboxyl group in the resin to −
CONH-CH ₂ CH ₂ - may also occur concatenation.

The above example is a case where all R ₁ and R ₂ are methyl groups and X and Y are ethylene groups in the above structural formula, but the present invention is not limited to these.
Each of the five R _{1 's} may be independently a hydrogen atom or a methyl group, and specific examples of R ₂ include, for example, a methyl group, an ethyl group, an n- or iso-propyl group, n-, i
a so- or tert-butyl group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted benzyl group and the like;
Specific examples of Y and Y include an ethylene group, a propylene group, a diethylene group, a 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, and more preferably 20,000 to 40,000 in terms of polystyrene equivalent number average molecular weight.

[0021]An alkylene oxide chain or a formula in the structure
Polyfunctional monomer containing a skeleton represented by the structural formula (2)
ー In the structure, an alkylene oxide chain or a structure of the formula (2)
The polyfunctional monomer containing the skeleton represented by the formula
Contains relatively long chains between groups, i.e., spacer components
Therefore, the urethane-modified polymer represented by the structural formula of the above formula (1)
Of the present invention in order to adjust the crosslinking reactivity with the cryl resin.
It is essential to be included in the photocurable resin composition.

In order to sufficiently crosslink the urethane-modified acrylic resin of the above formula (1), the urethane-modified acrylic resin is represented by an alkylene oxide chain having a spacer component of an appropriate length in the structure or the structural formula of the above formula (2). It is important to increase the reactivity by using a polyfunctional monomer having a skeleton containing the skeleton, to form a network easily, and to perform crosslinking. A polymer cross-linked by using such a component becomes a strong and stable film because it has a sufficient cross-linking density.

Organic Solvent The photocurable resin composition of the present invention comprises the above urethane-modified acrylic resin as a main component of a film-forming component, a releasing agent, and an alkylene oxide chain or a compound represented by the formula (1) in the structure. These components are used together with a polyfunctional monomer having a skeleton represented by the following structural formula in a form dissolved in an appropriate organic solvent. As such an organic solvent, any organic solvent that dissolves the urethane-modified acrylic resin as described above may be used.However, in consideration of coating properties and drying properties, toluene, an aromatic solvent such as xylene, Examples include ketone solvents such as acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone, and cyclohexanone, and cellosolve organic solvents such as methyl cellosolve and ethyl cellosolve. A mixed solvent composed of these solvents is particularly preferably used. The solid content concentration of the urethane-modified acrylic resin in the photocurable resin composition of the present invention is not particularly limited, but is generally preferably in the range of about 1 to 50% by weight on a weight basis.

Release Agent It is essential that the photocurable resin composition of the present invention contains a release agent. As the release agent used in the present invention, conventionally known release agents, for example, solid wax such as polyethylene wax, amide wax, Teflon (registered trademark) powder, fluorine-based or phosphate-based surfactant, silicone, etc. Can be used. Particularly preferred release agents are modified silicones, and specific examples thereof include the following 1) to 7). 1) Modified silicone oil side chain type 2) Modified silicone oil both terminal type 3) Modified silicone oil single terminal type 4) Modified silicone oil side chain both terminal type 5) Methylpolysiloxane containing trimethylsiloxysilicic acid (with silicone resin) 6) Silicone graft acrylic resin 7) Methyl phenyl silicone oil Modified silicone oil is classified into reactive silicone oil and non-reactive silicone oil. Reactive silicone oils include amino-modified, epoxy-modified, carboxyl-modified, carbinol-modified, methacryl-modified,
Mercapto modification, phenol modification, single-terminal reactivity, heterofunctional group modification and the like. Non-reactive silicone oils include polyether modified, methylstyryl modified, alkyl modified, higher fatty ester modified, hydrophilic special modified,
Higher alkoxy modification, higher fatty acid modification, fluorine modification and the like. Among the above silicone oils, a reactive silicone oil of a type having a group that is reactive with a film-forming component reacts with and binds to the resin as the resin layer cures, so that the surface of the resin layer on which a concavo-convex pattern is formed later Characteristic performance without bleed-out. In particular, it is effective for improving the adhesion to the deposition layer in the deposition step.

In the present invention, the photocurable resin composition (paint) of the present invention is applied on a substrate such as a polyester film to form a photocurable resin layer. After applying various concavo-convex patterns, the resin layer is cured by exposing to ultraviolet rays or electron beams, and then a layer having a different metal index or a refractive index is laminated on the formed concavo-convex pattern surface, such as a diffraction grating or a relief hologram. It can be.

Therefore, when the step of coating (coating and drying) the composition onto a film and the step of copying a hologram or the like are performed in separate steps, if the surface of the coating film formed by coating has a tack, When the film having the coating film is directly wound into a roll, blocking occurs, which is inconvenient. Coating and drying using a solvent system that is localized on the surface side of the coating layer at the time of coating and drying is effective in preventing the above-mentioned blocking, and also effective in increasing the repetitive embossing property during duplication. It is. When the surface of the coating film has a tack, a method of laminating a release film on the coating film surface and then winding the film can be selected. When the coating (coating and drying) process of the composition onto a film and the replication process of a hologram or the like are performed in a continuous process, the above-mentioned constraints are relaxed.

In the present invention, by including a release agent (particularly silicone) as described above in the photocurable resin composition, for example, when a diffraction grating or the like is produced by embossing, a press stamper of the diffraction grating can be used. Improves the peelability of the photocured resin layer, prevents contamination of the press stamper,
The press stamper can be used continuously for a long period of time (this is called repetitive embossability).

The release agent is used in an amount of about 0.1 to 50 parts by weight, preferably about 0.5 to 10 parts by weight, per 100 parts by weight of the urethane-modified acrylic resin. If the amount of the release agent used is less than the above range, peeling between the press stamper and the photocurable resin layer is insufficient, and it is difficult to prevent contamination of the press stamper. On the other hand, if the amount of the release agent exceeds the above range, a problem of surface roughness of the coating film surface due to repelling at the time of application of the composition occurs, or a substrate itself and an adjacent layer in the product, for example, a vapor deposition layer It is not preferable in that the adhesion is impaired and the film is broken at the time of transfer (the film strength becomes too weak).

In order to adjust the flexibility and the crosslink density of the resin layer obtained after curing the other constituent components , a usual thermoplastic resin, an acrylic resin, other monofunctional or Polyfunctional monomers, oligomers and the like can be included.

For example, monofunctional monofunctional (meth) acrylates such as tetrahydrofurfuryl (meth) acrylate, hydroxyethyl (meth) acrylate, vinylpyrrolidone, (meth) acryloyloxyethyl succinate, (meth) acryloyloxyethyl phthalate, etc. No.

When the components having two or more functional groups are classified by skeleton structure, polyol (meth) acrylate (epoxy-modified polyol (meth) acrylate, lactone-modified polyol (meth) acrylate, etc.), polyester (meth) acrylate, epoxy (meth) acrylate , Urethane (meth) acrylates, and other polybutadiene-based, isocyanuric acid-based, hydantoin-based, melamine-based, phosphoric acid-based, imide-based, and phosphazene-based poly (meth) acrylates; A variety of monomers, oligomers, and polymers are available.

More specifically, bifunctional monomers or oligomers include polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, and 1,6-hexanediol di ( Meth) acrylates, etc., and trifunctional monomers, oligomers, and polymers include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, and aliphatic tri (meth) acrylate. As monomers and oligomers, pentaerythritol tetra (meth) acrylate,
Ditrimethylolpropane tetra (meth) acrylate, aliphatic tetra (meth) acrylate and the like,
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.

The number of functional groups in the polyfunctional monomer or oligomer is not particularly limited. However, if the number of functional groups is smaller than 3, heat resistance tends to decrease.
If it exceeds 3, the flexibility tends to decrease.
Those having 20 functions are preferred.

The amount of the polyfunctional monomer or oligomer used is in the range of about 5 to 40 parts by weight, preferably about 10 to 3 parts by weight, per 100 parts by weight of the urethane-modified acrylic resin.
Use in the range of 0 parts by weight. If the amount of the polyfunctional monomer or oligomer used is less than the above range, the strength, heat resistance, scratch resistance, water resistance, chemical resistance, and adhesion to the substrate of the obtained photocurable resin layer cannot be said to be sufficient. If the amount of the polyfunctional monomer or oligomer exceeds the above range, the surface tack becomes high, causing blocking, or a part of the material remaining on the plate (press stamper) at the time of duplicating a hologram or the like (plate removal). It is not preferable in that the repetitive embossability is lowered.

Photosensitizer and Other Auxiliaries In the present invention, when the photocurable resin composition is cured by ultraviolet rays, it is necessary to add a photosensitizer to the composition. In the case of curing with an electron beam, a photosensitizer is unnecessary. Examples of the photosensitizer include various photosensitizers used as photosensitizers in conventional UV-curable paints, for example, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, α-methylbenzoin. And benzoin compounds such as α-phenylbenzoin; anthraquinone compounds such as anthraquinone and methylanthraquinone; benzyl ketone compounds such as acetylphenone and benzophenone; sulfide compounds such as diphenyl disulfide and tetramethylthiuram sulfide; α-chloromethyl Naphthalene; halogenated hydrocarbons such as anthracene, hexachlorobutadiene and pentachlorobutadiene; Such a photosensitizer is preferably used in an amount of about 0.5 to 10 parts by weight per 100 parts by weight of the urethane-modified acrylic resin.

The photocurable resin composition of the present invention may further comprise, in addition to the above components, phenols such as hydroquinone, t-butylhydroquinone, catechol and hydroquinone monomethyl ether; quinones such as benzoquinone and diphenylbenzoquinone; phenothiazines Addition of a polymerization inhibitor such as copper improves storage stability. Further, various assistants such as an accelerator, a viscosity modifier, a surfactant, an antifoaming agent, and a silane coupling agent may be added, if necessary.
It is also possible to blend a polymer such as styrene / butadiene rubber.

Applications and Modes of Application of the Photocurable Resin Composition The uses of the photocurable resin composition of the present invention will be described with reference to some examples. The photocurable resin composition is coated or impregnated on a base material such as a metal plate, paper, or polyethylene terephthalate, and then set at a temperature at which the organic solvent contained in the composition flies, for example, 100 to 165 ° C. The photocurable resin layer is formed on the substrate by introducing into a heated furnace for about 6 seconds to 1 minute and drying.

Then, for example, in this photocurable resin layer,
A desired hologram relief is patterned (embossed) using a press stamper, and then the resin layer is photo-cured by irradiating ultraviolet rays, an electron beam, or the like.

Since the obtained hologram is generally of a transmission type, it is necessary to provide a reflection layer. When a metal thin film that reflects light is used as the reflective layer, an opaque hologram is formed. When a transparent substance has a refractive index difference from the hologram layer, the hologram becomes a transparent hologram, and any of them can be used in the present invention. Reflective layer, sublimation, vacuum deposition, sputtering,
It can be formed by a known method such as 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 solely or in combination of two or more kinds of such metals and their oxides and nitrides. 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 a 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.

More specifically, the hologram pattern
For embossing, for example, attach a press stamper to the peripheral surface
Pair of embossed metal roll and paper roll
In the usual way using srolls, for example 50 to 15
0 ° C, 10-50 kg / cm ^TwoAt a pressure of Emboss
One-sided embossing is sufficient for processing, but double-sided embossing
Good.

In embossing, it is important to set the temperature of the embossing roll. From the viewpoint of reproducing the embossed shape, it is better to emboss at a relatively high temperature and a relatively high pressure, in order to prevent adhesion to the embossing plate. Has a relationship completely opposite to the relationship between the temperature and the pressure. Also, when considering the heat capacity that works effectively, the transport speed of the film to be copied is also important. In order to reduce the adhesion of the resin composition to the embossing roll, it is important to select the above-described release agent.

Further, by using the photocurable resin composition of the present invention, the photocurable resin composition is applied to the surface of a substrate which has been subjected to offset printing in advance, and after drying, the photocurable resin composition is embossed. After that, it is light-cured to form a relief, so that a three-dimensional map or poster can be manufactured.

Further, a photocurable resin composition is applied on a first base material such as a release film made of polyethylene terephthalate, dried, and thereafter, a pattern is printed on the photocurable resin layer, and then on the printed surface. After applying hot stamping agent, plywood, A
A second base material such as a BS sheet or a zinc plate was stuck on the hot stamping agent surface, the resin layer printed on the second base material was transferred by a heat transfer roll or the like, and the release film was removed and exposed. By photo-curing the photo-curable resin layer, it is possible to produce a film, a metal plate, or the like in which a pattern is transferred to a substrate.

The light used for curing the photocurable resin composition of the present invention includes high energy ionizing radiation and ultraviolet light. As the high-energy ionizing radiation source, for example, an electron beam accelerated by an accelerator such as a Cockcroft type accelerator, a Handigraf type accelerator, a linear accelerator, a betatron, or a cyclotron is industrially most conveniently and economically used. However, other radiation such as radioisotopes, γ-rays, X-rays, α-rays, neutrons, and protons emitted from a nuclear reactor or the like can also be used. Examples of the ultraviolet light source include an ultraviolet fluorescent lamp, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a xenon lamp, a carbon arc lamp, and a sun lamp.

Hologram Duplicating Apparatus FIG. 1 shows a configuration example of the hologram duplicating apparatus. The hologram duplication device 10 of FIG. 1 includes a sheet feeding device 20, a transfer device 30, and a pair of main body frames 12 fixed to a bed 13.
An irradiation device 50 and a winding device 60 are sequentially provided. A take-up roll 21 on which the hologram-forming film 1 is wound is mounted on the paper feeding device 20. The transfer device 30 is provided with a pressing roller 40 capable of heating and pressing the hologram forming film 1 fed from the sheet feeding device 20 and an emboss roller 31 having a hologram master provided on a surface thereof. The irradiation device 50 can cure the hologram layer by irradiating the hologram-forming film 1 sent from the transfer device 30 with ultraviolet light or an electron beam. The winding device 60 can wind the hologram sheet in which the hologram layer has been cured.

The embossing roller 31 of the hologram duplication device 10 is provided with a press stamper continuously produced from a master hologram produced by using a laser beam. A duplicate hologram prepared from a master hologram on a resin plate and attached to a cylinder can also be used.

[0049]

Next, the present invention will be described more specifically with reference to examples and comparative examples. The parts or percentages in the examples are on a weight basis unless otherwise specified.

Example 1 Production of Urethane-Modified Acrylic Resin The production of the urethane-modified acrylic resin used in this example is described below.

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 methyl ethyl ketone (abbreviation: MEK) were charged together with an azo-based polymerization initiator, and 2-hydroxyethyl methacrylate (abbreviation: HEMA) 22.4 g, a mixed solution of methyl methacrylate (abbreviation: MMA) 70.0 g, toluene 20 g, and MEK 20 g was dropped through a dropping funnel over about 2 hours, and reacted at a temperature of 100 to 110 ° C. for 8 hours. Then, it was cooled to room temperature.

In addition, 2-isocyanatoethyl methacrylate (Karenz MOI: trade name, manufactured by Showa Denko) 2
A mixed solution of 7.8 g of toluene 20 g and MEK 20 g 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, the reaction was terminated, and a urethane-modified acrylic resin solution used in Example 1 was obtained. The solid content of the obtained urethane-modified acrylic resin solution is 41.0%.
%, The viscosity is 130 mPa (300 ° C.), the molecular weight is 35,000 in terms of polystyrene, and the amount of C ＝ C bond introduced is 13.8.
Mol%. Preparation of Photocurable Resin Compositions The following five types of photocurable resin compositions A to E of Example 1 were prepared using the urethane-modified acrylic resin solution obtained in the above step.

Preparation of photocurable resin composition A: urethane-modified acrylic resin solution (solid content basis) 100 parts Silicone: trimethylsiloxysilicate-containing methylpolysiloxane (trade name: KF-7312, manufactured by Shin-Etsu Chemical Co., Ltd.) 1 part Multifunctional monomer [trade name: KAYARAD DPCA-20, manufactured by Nippon Kayaku Co., Ltd. The structural formula is shown in the following formula (3). In the formula, m (average) = 1, a (average) = 2, b (average) = 4; average molecular weight is 806. 10 parts Photosensitizer (trade name: Irgacure 907, manufactured by Ciba Specialty Chemicals) 5 parts These components are diluted with methyl ethyl ketone (MEK) to adjust the solid content of the composition to 50%, and the photocurable resin is cured. Composition A was used.

[0054]

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Preparation of photocurable resin composition B: urethane-modified acrylic resin solution (solid content basis) 100 parts Silicone: amino-modified reactive silicone oil (both terminal type) (trade name: KF-8012, Shin-Etsu Chemical Co., Ltd.) 1 part, polyfunctional monomer [trade name: KAYARAD DPCA-30, manufactured by Nippon Kayaku Co., Ltd. The chemical structural formula is m (average) = 1, a (average) = 3, b ( (Average) = 3; average molecular weight 920. 20 parts Photosensitizer (trade name: Irgacure 651, manufactured by Ciba Specialty Chemicals Co., Ltd.) 5 parts These components are diluted with methyl ethyl ketone (MEK) to adjust the solid content of the composition to 50%. Composition B was used.

Preparation of photocurable resin composition C: urethane-modified acrylic resin solution (solid content basis) 100 parts Silicone oil: amino-modified reactive silicone oil (side chain type) (trade name: KF-860, Shin-Etsu Chemical) 1 part polyfunctional monomer [trade name: KAYARAD DPCA-60, manufactured by Nippon Kayaku Co., Ltd.] The chemical structural formula is m (average) = 1, a (average) = 6, b in the above formula (3). (Average) = 0; average molecular weight 1262. 15 parts Photosensitizer (trade name: Irgacure 907, manufactured by Ciba Specialty Chemicals) 5 parts These components are diluted with methyl ethyl ketone (MEK) to adjust the solid content of the composition to 50%, and photocurable. Resin composition C was obtained.

Preparation of photocurable resin composition D: urethane-modified acrylic resin solution (solid content basis) 100 parts Silicone oil: amino-modified reactive silicone oil (one-end type) (trade name: KF-8012, Shin-Etsu Chemical) 1 part polyfunctional monomer [trade name: KAYARAD DPCA-120, manufactured by Nippon Kayaku Co., Ltd.] The chemical structural formula in the above formula (3) is m (average) = 2, a (average) = 6, b (Average) = 0; average molecular weight is 1947. 20 parts Photosensitizer (trade name: Irgacure 907, manufactured by Ciba Specialty Chemicals) 5 parts These components are diluted with methyl ethyl ketone (MEK) to adjust the solid content of the composition to 50%, and the photocurable resin is cured. Composition D was used.

Preparation of photocurable resin composition E: urethane-modified acrylic resin solution (solid content basis) 100 parts methacryl-modified silicone oil (trade name: X-22-164B, manufactured by Shin-Etsu Chemical Co., Ltd.) 3 parts Functional monomer (trade name: KAYARAD DPCA-60, manufactured by Nippon Kayaku Co., Ltd.) 15 parts Photosensitizer (trade name: Irgacure 651, manufactured by Ciba Specialty Chemicals Co., Ltd.) 5 parts These components are diluted with methyl ethyl ketone (MEK). The photocurable resin composition E was prepared by adjusting the composition to 50%.

Embodiments 2 to 6 Copy of hologram The hologram of the embodiments 2 to 6 was copied by a hologram copying apparatus shown in FIG. More specifically,
A continuous duplication apparatus described in detail in Japanese Patent Application Laid-Open No. 61-156273 was used.

Each of the five types of photocurable resin compositions A to E prepared in Example 1 was treated with a 50 μm single-sided easy-adhesion treated polyethylene terephthalate film (trade name: Diafoil T-600, manufactured by Diafoil Hoechst Co., Ltd.). ) Is coated on the easily-adhesive treated surface at a speed of 20 m / min with a roll coater, dried at 100 ° C. to evaporate the solvent, and then a 2 g / m ² copy photosensitive film with a dry film thickness is applied. Obtained. Each of the obtained films was not sticky at room temperature and could be stored in a wound state.

Each photosensitive film for duplication prepared above was set on the paper feeding 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 reflective relief hologram.

On this surface, an adhesive layer (trade name: Nissetsu PE-118 + CK101, manufactured by Nippon Carbide Co., Ltd.) was applied by roll coating, dried at 100 ° C. to evaporate the solvent, and then treated with silicone as a release film. A PET film (trade name: SPO5, manufactured by Tokyo Cellophane Paper Co., Ltd.) was laminated to obtain an adhesive layer having a dry film thickness of 25 g / m ² . Each of the obtained hologram sheets is in the form of a label, and can be used for a printed matter or display that displays a three-dimensional image.

Embodiments 7 to 11 Manufacturing of Diffraction Gratings The same diffraction grating duplication apparatus as that shown in the above-described Embodiments 2 to 6 used for hologram duplication was used. Was manufactured.

Each of the five types of photocurable resin compositions was applied to a 50 μm single-sided easy-adhesion treated polyethylene terephthalate film (trade name: Diafoil T-600, manufactured by Diafoil Hoechst) at 20 m / m mi
After coating with a roll coater at a speed of n and 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. Each of the obtained films was not sticky at room temperature and could be stored in a wound state.

A press stamper continuously formed from a master diffraction grating drawn by using an electron beam is installed on an emboss roller of the copying apparatus. A duplicated diffraction grating prepared from a master diffraction grating on a resin plate and attached to a cylinder can also be used.

Each of the photosensitive films for duplication prepared above was placed on the picture paper 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 vapor-deposited thereon by a vacuum vapor deposition method to form each reflection grating.

An adhesive layer (trade name: Nissetsu PE-118 + CK101, manufactured by Nippon Carbide Co., Ltd.) was applied on this surface by roll coating, dried at 100 ° C. to evaporate the solvent, and then treated with silicone as a release film. A PET film (trade name: SPO5, manufactured by Tokyo Cellophane Paper Co., Ltd.) was laminated to obtain an adhesive layer having a dry film thickness of 25 g / m ² .
Each of the obtained diffraction grating sheets is in the form of a label, and can be used for a printed matter that displays a three-dimensional image, a display, and the like.

[Examples 12 to 16] Production of hologram by transfer method A 25 μm polyethylene terephthalate film (trade name: Lumirror T60, manufactured by Toray Industries) was coated with a release layer at a speed of 20 m / min by gravure coating. After drying at 0 ° C. to evaporate the solvent, a film having a dry film thickness of 1 g / m ² and a layer structure of PET / PET was obtained.

The release layer in the above is a layer which is transferred to the surface of the object to be transferred and becomes the outermost surface after the transfer of the transfer foil, and is provided for the purpose of improving the releasability of the transfer layer and the cutting property of the foil. Various known materials can be used depending on the type of the base film. As the material of the release layer, for example, one or more of polymethacrylate resin, polyvinyl chloride resin, cellulose resin, silicone resin, chlorinated rubber, casein, various surfactants, metal oxides, and the like can be used. A mixture is used.

In particular, the release layer is preferably formed by appropriately selecting its material and the like so that the release force between the base film and the transfer layer is 1 to 5 g / inch (90 ° release). This release layer can be formed on the surface of the substrate film by a known method such as ink formation and coating, and its thickness is preferably in the range of 0.1 to 2 μm in consideration of the release force, foil breakage and the like.

The above five photocurable resin compositions A of the present invention
To E on a release layer of a film having a layer configuration of release layer / PET, coated with a roll coater, dried at 100 ° C. to evaporate the solvent, and then duplicated at a dry film thickness of 2 g / m ² . A photosensitive film for use was obtained. Each of the obtained films was sticky at room temperature and could be stored in a wound state.

A press stamper continuously produced from a master hologram produced by using a laser beam is provided on the emboss roller of the copying apparatus. A duplicate hologram prepared from a master hologram on a resin plate and attached to a cylinder can also be used. Place each of the photosensitive films for duplication prepared above on the picture paper side.
It was heated and pressed at 50 ° 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 each reflection type relief hologram. On this surface, an adhesive layer was applied by gravure coating, dried at 100 ° C. to evaporate the solvent, and then an adhesive layer having a dry film thickness of 1 g / m ² was obtained.

As the material of the adhesive layer, a known heat-sensitive adhesive resin can be used. For example, rubbers such as polyisoprene rubber, polyisobutylene rubber, styrene butadiene rubber, poly (meth) methyl acrylate, poly (meth) ethyl acrylate, poly (meth) acrylate, propyl (poly (meth) acrylate), (Meth) acrylates such as 2-ethylhexyl poly (meth) acrylate, polyvinyl ethers such as polyisobutyl ether, polyvinyl acetate such as polyvinyl acetate, vinyl chloride-vinyl acetate copolymer, polyacrylamide, polymethylol Polyamides such as acrylamide,
Examples thereof include vinyl chloride such as polyvinyl chloride, polystyrene, polyester, polychlorinated olefin, polyvinyl butyral, and vinyl acetate / octyl acrylate, vinyl acetate / butyl acrylate, and vinylidene chloride / butyl acrylate.

The film to be coated may be any film having a transfer property and a peeling property. For example, a biaxially stretched polyethylene terephthalate (PET) film may have a dimensional stability, a heat resistance and a toughness. Most preferred from the point of view.
Other than this, polyvinyl chloride film, polypropylene film, polyethylene film, polycarbonate film, cellophane, polyvinyl alcohol film,
Acetate films, nylon films, polyamide films, polyamide-imide films, ethylene / vinyl alcohol copolymer films, fluorine-containing films, various co-extruded films, and the like can be used. 5μ in thickness
m to 200 μm, preferably 10 μm to 50 μm.

Thermal transfer was performed on a plywood with a heat roll from the film side with the acrylic adhesive side down.
Next, the release film was peeled off, and the resin of the surface layer was cured by irradiating ultraviolet rays generated from a mercury lamp. It is in the form of a transfer foil and can be used for printed matter, displays, etc. that project a three-dimensional image. When heat transfer was performed on a vinyl chloride card with a transfer machine, it was found that the foil cut was good and the adhesion was excellent.

Table 1 shows the physical properties of the processed products of Examples 2 to 16 described above.

Comparative Example 1 The same amount of polyfunctional monomer (trade name: Light Ester H, manufactured by Kyoei Chemical Co., Ltd .; A compound F having the same composition as the composition A is prepared using the compound represented by the formula), and a hologram is formed by using the composition F in the same manner as described above. Done. Table 1 shows the physical properties of these processed products.

[0078]

Embedded image

[0079]

[Table 1]

The method for evaluating physical properties is as follows. Peeling property (peeling property from press stamper): The coating film was subjected to continuous copying for 1000 m using the copying machine shown in FIG. 1 to check whether there was any residual resin on the press stamper.・ ・ ・: There is no remaining. ×: There is a remainder.

Chemical resistance: When the cured surface of the processed product was rubbed by reciprocating 100 times with gauze impregnated with methyl ethyl ketone, those having no abnormality on the surface were regarded as good, and those having abnormality on the surface were regarded as defective. did.・ ・ ・: Good. ×: defective.

Heat resistance: The cured surface of the processed product is
Discoloration and deformation after heating to 00 ° C. and holding for 3 minutes were observed. Those having no abnormality were evaluated as good, and those having yellowing, deformation or peeling were evaluated as defective.・ ・ ・: Good. ×: defective.

Scratch resistance: When the cured surface of the processed product was rubbed 10 times with # 0000 steel wool, the one with no change in the surface was regarded as good, and the one with scratched and whitened surface was regarded as defective.・ ・ ・: Good. ×: defective.

Suitability for evaporation: After an aluminum layer was evaporated on the hologram or diffraction grating forming surface by a vacuum evaporation method, the adhesion was evaluated by a cellotape (registered trademark) grid test.・ ・ ・: Good vapor deposition property. ×: Poor deposition property.

Transfer foil suitability: After depositing an aluminum layer on the hologram or diffraction grating formation surface by vacuum deposition,
Further, an acrylic adhesive (hot stamping agent) for heat sealing is applied and the resultant is transferred onto a polyvinyl chloride card using a transfer machine, and the cut-off property and adhesion of the transfer foil are evaluated. did.・ ・ ・: Good. ×: defective.

Bending resistance: The transfer foil transferred onto the polyvinyl chloride card was embossed into letters to check whether the embossed letters were cracked or the like.・ ・ ・: No change. ×: There are cracks.

[0087]

According to the photocurable resin composition of the present invention,
Excellent strength, heat resistance and scratch resistance by containing urethane-modified acrylic resin of specific structure; release agent; and polyfunctional monomer containing alkylene oxide chain or skeleton of specific structure in the structure as essential components It is possible to form a diffraction grating or a relief hologram that can form a film having water resistance, chemical resistance, and adhesion to a substrate, and also has the ability to follow the flexibility and expansion and contraction of an adherend.

The photocurable resin composition of the present invention contains an alkylene oxide chain or a polyfunctional monomer having a skeleton represented by the above formula (2) in its structure. When the urethane-modified acrylic resin of the formula (1) contained in the product is crosslinked, the reactivity can be increased, a network can be easily formed, and crosslinking can be performed. The obtained film has a sufficient cross-linking density and is therefore firm and stable.

[Brief description of the drawings]

FIG. 1 shows a configuration example of a hologram duplication device.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Hologram forming film 10 Hologram duplication device 12 Main body frame 13 Bed 20 Paper feed device 21 Winding roll 30 Transfer device 31 Emboss roller 40 Pressing roller 50 Irradiating device 60 Winding device

──────────────────────────────────────────────────続 き Continuation of the front page (51) Int.Cl. ⁷ Identification symbol FI G03H 1/20 G03H 1/20 (56) References JP-A-2000-273129 (JP, A) JP-A-2000-272295 (JP, A JP-A-2000-226421 (JP, A) JP-A-2000-103826 (JP, A) JP-A-7-304288 (JP, A) JP-A-2001-31729 (JP, A) JP-A-11-342221 (JP) JP-A-2000-63459 (JP, A) JP-A-11-292930 (JP, A) JP-A-2000-63460 (JP, A) JP-A-2000-63458 (JP, A) JP-A-2000-63461 (JP, A) JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08F 290/00-290/14 C08F 299/00-299/08 G02B 5/18 G02B 5/32 G03F 7/027 G03H 1 / 20

Claims (10)

(57) [Claims] 1. A urethane-modified acrylic resin represented by the following structural formula: (In the formula, five R _{1 s} each independently represent a hydrogen atom or a methyl group, R ₂ represents a C ₁ -C ₁₆ hydrocarbon group, and X and Y represent a linear or branched alkylene. When the sum of l, m, n and o is 100,
1 is an integer of 20 to 90, m is an integer of 0 to 50, n is an integer of 10 to 80, and o is an integer of 0 to 20. ); A release agent; and a polyfunctional monomer having an alkylene oxide chain or a skeleton represented by the following structural formula in the structure: (Wherein, R ₁ is a linear or branched alkylene group having 2 to 8 carbon atoms, and n is an integer of 20 or less). object. 2. The photocurable resin composition according to claim 1, wherein the release agent is contained in a ratio of 0.1 to 50 parts by weight per 100 parts by weight of the resin. 3. The photocurable resin composition according to claim 1, wherein the release agent is a modified silicone oil. 4. The photocurable resin composition according to claim 3, wherein the modified silicone oil is a reactive silicone oil. 5. The resin according to claim 1, wherein the polyfunctional monomer is a resin 1.
The photocurable resin composition according to claim 1, which is contained in a proportion of 1 to 50 parts by weight per 00 parts by weight. 6. The photocurable resin composition according to claim 1, wherein the resin has an arithmetic average molecular weight of 10,000 to 200,000 in terms of polystyrene. 7. The photocurable resin composition according to claim 1, comprising a polyfunctional monomer or a polyfunctional oligomer. 8. The photocurable resin composition according to claim 1, applied to at least one surface of a substrate, and then dried to form a photocurable resin layer. A method for forming a concavo-convex pattern, comprising embossing a surface of the photocurable resin layer, and exposing the resin layer to cure the resin layer. 9. The method for forming a concavo-convex pattern according to claim 8, wherein the exposing is performed with an ultraviolet ray or an electron beam. 10. The method according to claim 8, wherein the uneven pattern is a diffraction grating or a relief hologram.