JP3527651B2 - Photocurable resin composition and method of forming uneven pattern - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a photocurable resin composition and a method for forming a concavo-convex pattern, and more particularly to a urethane-modified acrylic resin capable of forming a coating having heat resistance and flexibility at the same time. The present invention relates to a photocurable resin composition as a film-forming component and a method for forming an uneven pattern such as a diffraction grating or a relief hologram.

[0002]

2. Description of the Related Art Conventionally, a photocurable resin composition (paint) is
For example, a photo-curable resin layer is formed by coating on a substrate such as polyester film, various concave and convex patterns are applied to the photo-curable resin layer, and then exposed by irradiation with ultraviolet rays or electron beams, A method is used in which a resin layer is cured, and then a metal film or layers having different refractive indexes are laminated on the surface of the uneven pattern formed to form a diffraction grating or a relief hologram.

As a method of applying the above-mentioned uneven pattern,
For example, in the case of forming a relief hologram, a press stamper (hereinafter simply referred to as a press stamper) prepared from a master hologram on which a desired concavo-convex pattern is formed is prepared, and this press stamper is used as the photocurable resin layer. Then, pressure is applied (embossing) to transfer the embossed pattern of the press stamper to the resin layer, and the resin layer is cured by exposing in that state to fix the embossed pattern. When a large number of relief holograms are formed in this way, a large number of embossing processes are performed with a single press stamper.

[0004]

Since the above-mentioned conventional photo-curable paints are liquid in many cases, the storage stability of the paints is poor, and there is concern about the quality stability of the resulting concave-convex pattern such as holograms. . In addition, when a conventional photo-curable paint is used, many additives are mixed in the paint, so 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 damaged, and the quality of similarly obtained holograms becomes unstable.

Diffraction gratings and relief holograms have been conventionally used for the purpose of decorating various cards and securities and for the purpose of preventing forgery, but with the expansion of their applications, they are further excellent in strength, heat resistance, scratch resistance, and water resistance. Properties, chemical resistance, and adhesion to a base material are required, and flexibility to the adherend and conformability to expansion and contraction are required. Particularly in the case of a diffraction grating or relief hologram made of conventional photo-curable paint, the resin used loses flexibility due to photo-curing, and as a result, bending or stretching of the adherend results in a diffraction grating or relief hologram. Was lost.

In order to solve these problems, the inventor of the present applicant has been excellent in using the material system as disclosed in JP-A-61-156273 and JP-B-5-54502. Diffraction gratings and relief holograms that can form coatings with strength, heat resistance, scratch resistance, water resistance, chemical resistance, and adhesion to base materials, and also have flexibility with respect to the flexibility and expansion and contraction of the adherend It has succeeded in providing a photocurable resin composition capable of forming a resin.

However, the above-mentioned JP-A-61-1562 is used.
The reactive resin described in Japanese Patent Publication No. 73 is a system in which hydroxyethyl methacrylate is added to a resin having a hydroxyethyl methacrylate unit in its main chain via diisocyanate again to introduce a double bond into the resin. However, it is difficult to introduce a double bond into the resin as designed, and there is a problem that the resin tends to gel due to the influence of a trace amount of water in the system. Further, the reactive resin described in JP-B-5-54502 has a melamine skeleton and thus is slightly inferior in water resistance. Further, when there is a methylol group, formaldehyde is generated by hydrolysis. Had. Therefore, the object of the present invention is to form a coating having excellent strength, heat resistance, scratch resistance, water resistance, chemical resistance, and adhesion to a substrate, and to follow the flexibility and expansion / contraction of an adherend. It is an object of the present invention to provide a photocurable resin composition capable of forming a diffraction grating, a relief hologram, and the like which also have properties.

[0008]

The above object can be achieved by the present invention described below. That is, the present invention contains a urethane-modified acrylic resin represented by the following structural formula, a release agent, and urethane acrylate as essential components, and the urethane acrylate has two or more isocyanate groups. Urethane acrylate having a molecular weight of 500 to 50,000 obtained by reacting a cyanate compound with an acrylate or methacrylate having 1 to 4 hydroxyl groups and 1 to 5 acryloyl groups or methacryloyl groups, or 2
The molecular weight obtained by reacting an isocyanate compound having one or more isocyanate groups, a compound having 1 to 4 hydroxyl groups, and a compound having 1 to 2 hydroxyl groups and 1 to 5 acryloyl groups or methacryloyl groups is Fifty
It is a photocurable resin composition characterized by being 0-50,000 urethane acrylate. (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 are linear or branched. Represents an alkylene group, where the sum of l (el), m, n, and o (o) is 100.
In this case, l is 20 to 90, m is 0 to 50, and n is 1.
0 to 80 and o are integers of 0 to 20. )

According to the present invention, by using a specific urethane-modified acrylic resin as a main film forming component of a photocurable resin composition, excellent strength, heat resistance, scratch resistance, water resistance and chemical resistance can be obtained. PROBLEM TO BE SOLVED: To provide a photocurable resin composition capable of forming a film having adhesiveness and adhesion to a substrate, and capable of forming a diffraction grating, a relief hologram and the like having flexibility and flexibility of an adherend. can do.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in more detail with reference to the following preferred embodiments. The urethane-modified acrylic resin used in the present invention is, for example, as a preferred example, 20 to 90 mol of methyl methacrylate, 0 to 50 mol of methacrylic acid, and 2-hydroxyethyl methacrylate 1
An acrylic copolymer obtained by copolymerizing 0 to 80 mol with a resin obtained by reacting methacryloyloxyethyl isocyanate (2-isocyanatoethyl methacrylate) with the hydroxyl groups present in the copolymer. Is.

Therefore, it is not necessary for the methacryloyloxyethyl isocyanate to react with all the hydroxyl groups present in the copolymer, and at least one of the hydroxyl groups of the 2-hydroxyethyl methacrylate unit in the copolymer should be at least one.
It is sufficient that 0 mol% or more, preferably 50 mol% or more, react 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
A monomer having a hydroxyl group such as -hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate can also be used.

As described above, by utilizing a hydroxyl group existing in a hydroxyl group-containing acrylic resin, a resin composition containing a urethane-modified acrylic resin as a main component, in which a large number of methacryloyl groups are introduced into the molecule, can be used, for example. 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 it is possible to form a diffraction grating or the like which has a high crosslink density but is excellent in flexibility and heat resistance. .

The above urethane-modified acrylic resin is
Solvent capable of dissolving the copolymer, for example, toluene, keto
, Cellosolve acetate, dimethyl sulfoxide
Dissolve in a solvent such as
Liloyloxyethyl isocyanate is added dropwise and reacted.
The isocyanate group of the acrylic resin
Reacts with a hydroxyl group to form a urethane bond, and the urethane bond
It is possible to introduce a methacryloyl group into the resin via
Wear. Methacryloyloxyethyliso used at this time
The amount of cyanate used depends on the hydroxyl group of the acrylic resin and the isocyanate.
Isocyanate per mole of hydroxyl group in proportion to cyanate group
Group of 0.1 to 5 mol, preferably 0.5 to 3 mol.
It is the amount to be enclosed. The equivalent of the hydroxyl group in the resin
Use the above methacryloyloxyethyl isocyanate
When used, the methacryloyloxyethyl isocyanate
Anates also react with the carboxyl groups in the resin to produce --CO
NH-CH ₂CH ₂It is also possible that a-linkage occurs.

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 thereto.
Each R ₁ may independently be a hydrogen atom or a methyl group, and specific examples of R ₂ include, for example, a methyl group, an ethyl group, n- or iso-propyl group, n-, i.
Examples thereof include a so- or tert-butyl group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted benzyl group, and the like, X
Specific examples of Y and Y include ethylene group, propylene group,
Examples thereof include a diethylene group and a dipropylene group. The thus obtained urethane-modified acrylic resin used in the present invention has a total molecular weight of 10,000 to 200,000 in terms of polystyrene, and more preferably 12 to 40,000.

Next, a production example of the urethane-modified acrylic resin used in the present invention will be shown. Production Example 1 To 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 (MEK) were charged together with an azo-based initiator.
-Hydroxyethyl methacrylate (HEMA) 22.
A mixture of 4 g, 70.0 g of methyl methacrylate (MMA), 20 g of toluene and 20 g of MEK is added dropwise through a dropping funnel, and the temperature is dropped at 100 to 110 ° C. for about 2 hours.
After reacting at the temperature of 8 hours, it was cooled to room temperature. 27.8 g of 2-isocyanate ethyl methacrylate (Showa Denko, Karenz MOI), 20 g of propylene glycol monomethyl ether acetate and MEK.
20 g of the mixed solution was added, and an addition reaction was performed using dibutyltin laurate as a catalyst. 2 by IR analysis of the reaction product
After confirming the disappearance of the absorption peak at 200 cm ^-1, the reaction was terminated.

Production Example 2 40 g of propylene glycol monomethyl ether acetate and methyl ethyl ketone (MEK) were placed in a 2 liter four-necked flask equipped with a condenser, a dropping funnel and a thermometer.
40 g was charged together with an azo-based initiator, and 2-hydroxyethyl methacrylate (HEMA) 22.4 g, methyl methacrylate (MMA) 62.3 g, methacrylic acid (MAA) 7.4 g, propylene glycol monomethyl ether acetate 20 g and MEK 20 g were mixed. The liquid is passed through the dropping funnel, and is added dropwise for about 2 hours to 10
After reacting for 8 hours at a temperature of 0 to 110 ° C., it was cooled to room temperature. 27.8 g of 2-isocyanate ethyl methacrylate (Showa Denko, Karens MOI), propylene glycol monomethyl ether acetate 20
and a mixed solution of 20 g of MEK were added to carry out an addition reaction using dibutyltin laurate as a catalyst. IR of reaction product
The disappearance of the absorption peak at 2200 cm ^-1 was confirmed by analysis, and the reaction was terminated.

Production Example 3 50 g of propylene glycol monomethyl ether acetate and 50 g of MEK were charged together with an azo-based initiator in a 2 liter four-necked flask equipped with a condenser, a dropping funnel and a thermometer, HEMA 22.4 g and MMA 57.8.
A mixed solution of 5 g, 11.1 g of MAA, 20 g of propylene glycol monomethyl ether acetate, and 20 g of MEK was allowed to react for 8 hours at a temperature of 100 to 110 ° C. while being added dropwise for about 2 hours, and then cooled to room temperature. . 2-isocyanatoethyl methacrylate (Showa Denko, Karenz MOI) 27.8
g, a mixed solution of 20 g of propylene glycol monomethyl ether acetate and 20 g of MEK was added to carry out an addition reaction with dibutyltin laurate as a catalyst. The reaction was terminated after confirming the disappearance of the absorption peak at 2200 cm ^-1 by IR analysis of the reaction product.

Production Example 4 40 g of propylene glycol monomethyl ether acetate and 40 g of MEK were charged together with an azo-based initiator in a 2 liter four-necked flask equipped with a condenser, a dropping funnel and a thermometer, 33.6 g of HEMA and 53.4 of MMA.
g, MAA 7.4 g, propylene glycol monomethyl ether acetate 20 g, and MEK 20 g through a dropping funnel, while adding dropwise over about 2 hours.
After reacting for 8 hours at a temperature of 0 to 110 ° C., it was cooled to room temperature. To this, 41.7 g of 2-isocyanate ethyl methacrylate (Showa Denko, Karenz MOI), propylene glycol monomethyl ether acetate 20
and a mixed solution of 20 g of MEK were added to carry out an addition reaction using dibutyltin laurate as a catalyst. IR of reaction product
The disappearance of the absorption peak at 2200 cm ^-1 was confirmed by analysis, and the reaction was terminated.

Production Example 5 35 g of propylene glycol monomethyl ether acetate and 35 g of MEK were charged together with an azo-based initiator in a 2 liter four-necked flask equipped with a condenser, a dropping funnel and a thermometer, and 11.2 g of HEMA and 62.3 of MMA.
1 g of MA, 14.8 g of MAA, 20 g of propylene glycol monomethyl ether acetate, and 20 g of MEK through a dropping funnel, while being added dropwise over about 2 hours.
After reacting for 8 hours at a temperature of 00 to 110 ° C., it was cooled to room temperature. To this, 13.9 g of 2-isocyanatoethyl methacrylate (Showa Denko, Karenz MOI),
Propylene glycol monomethyl ether acetate 2
A mixed solution of 0 g and MEK 20 g was added, and an addition reaction was performed using dibutyltin laurate as a catalyst. Reaction product I
The disappearance of the absorption peak at 2200 cm ^-1 was confirmed by R analysis, and the reaction was terminated.

Production Example 6 To 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 and MM.
A mixture of 70.0 g of A, 20 g of toluene, and 20 g of MEK was added dropwise through a dropping funnel, and the mixture was allowed to react for 8 hours at a temperature of 100 to 110 ° C. for 8 hours, and then cooled to room temperature. 2-isocyanatoethyl methacrylate (Showa Denko, Karenz MOI) 27.8
g, a mixed solution of 20 g of toluene and 20 g of MEK was added, and an addition reaction was performed using dibutyltin laurate as a catalyst. The reaction was terminated after confirming the disappearance of the absorption peak at 2200 cm ⁻¹ by IR analysis of the reaction product. The raw material composition used in the production of the urethane-modified acrylic resin used in the present invention obtained above and the physical properties of the obtained resin are shown in Table 1 below.
Shown in.

Table 1 "C = C amount" in the table is the average number of double bonds in one molecule of the polymer. The molecular weight in the table is the molecular weight in terms of standard polystyrene measured by gel permeation chromatography (GPC) (solvent: tetrahydrofuran (THF)).

The photocurable resin composition of the present invention is characterized in that the above urethane-modified acrylic resin is dissolved as a main component of the film-forming component in a suitable organic solvent together with a release agent. The organic solvent used may be any organic solvent that dissolves the urethane-modified acrylic resin as described above, but in consideration of coatability and drying property,
Aromatic solvents such as toluene and xylene, acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone,
Examples thereof include ketone solvents such as cyclohexanone, and cellosolve organic solvents such as methyl cellosolve and ethyl cellosolve. In particular, a mixed solvent composed of these solvents is preferably used. The solid content concentration of the urethane-modified acrylic resin in the composition is not particularly limited, but is generally preferably in the range of about 1 to 50% by weight on a weight basis.

The photocurable resin composition of the present invention contains a release agent in addition to the urethane modified acrylic resin.
As the release agent used in the present invention, a conventionally known release agent,
For example, polyethylene wax, amide wax, solid wax such as Teflon powder, fluorine-based or phosphoric acid ester-based surfactants, and silicone can all be used. A particularly preferable releasing agent is a modified silicone, and specifically, 1) modified silicone oil side chain type, 2) modified silicone oil both ends type, 3) modified silicone oil one end type, 4) modified silicone oil side chain Examples thereof include both-end type, 5) methylpolysiloxane containing trimethylsiloxysilicic acid (referred to as silicone resin), 6) silicone graft acrylic resin, and 7) methylphenyl silicone oil.

The modified silicone oil is divided into reactive silicone oil and non-reactive silicone oil.
Examples of the reactive silicone oil include amino-modified, epoxy-modified, carboxyl group-modified, carbinol-modified, methacryl-modified, mercapto-modified, phenol-modified, one-end-reactive, and different functional 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, and fluorine modification.

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

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

Therefore, when the step of coating the composition with the film (coating and drying) and the step of replicating the hologram or the like are carried out in separate steps, there is tack on the surface of the coating film formed by coating. However, when the film having this 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 during coating and drying is effective in preventing the above blocking, and also effective in increasing the repetitive embossing property during replication. Is. When the surface of the coating film has tack, a method of laminating the releasable film on the surface of the coating film and then winding the film can be selected. When the steps of coating the composition on the film (coating and drying) and the step of replicating a hologram or the like are performed in a continuous process, the above constraint conditions are relaxed.

In the present invention, the release agent (particularly silicone) as described above is contained in the resin composition so that, for example, when a diffraction grating or the like is produced by embossing, it is photocured with the press stamper of the diffraction grating. The release property of the resin layer is improved, the press stamper is prevented from being contaminated, and the press stamper can be used continuously for a long period of time (this is called repetitive embossing property). 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, based on 100 parts by weight of the urethane-modified acrylic resin. When the amount of the release agent used is less than the above range, the release of the press stamper and the photocurable resin layer is insufficient, and it is difficult to prevent the press stamper from being contaminated. On the other hand, if the amount of the release agent used exceeds the above range, a problem of surface roughness of the coating film due to cissing at the time of coating the composition may occur, or the substrate itself and the adjacent layer in the product, for example, a vapor deposition layer It is not preferable in that the adhesiveness is hindered, or the film is broken at the time of transfer (the film strength becomes too weak).

[0029] To further adjust the flexibility and crosslink density of the resulting resin layer after curing, the photo-curable resin composition of the present invention, urethane acrylated bets are added. As the urethane acrylate used in the present invention, any acrylate having a urethane group in the molecule and having photopolymerizability can be used, but the following urethane acrylates are preferred. This urethane acrylate is obtained by reacting an isocyanate compound having 2 or more isocyanate groups, a compound having 1 to 4 hydroxyl groups, a compound having 1 to 2 hydroxyl groups and 1 to 5 acryloyl groups or methacryloyl. The obtained molecular weight is 500-
50,000 compounds.

The above-mentioned isocyanate compound is an aliphatic or aromatic isocyanate compound having 2 or more, preferably 2 to 3 isocyanate groups in the molecule,
For example, tetramethylene diisocyanate, hexamethylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-
Diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, 3,3-dimethyl-4,4'-diphenylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, 1,3-bis (isocyanite methyl) cyclohexane, trimethylhexamethylene diisocyanate, hydrogen Added xylylene diisocyanate or the following general formula OCNR ₁ NCO or R _2- (NCO) ₃ (wherein R ₁ is a hydrocarbon group having 1 to 14 carbon atoms, R ₂ is an isocyanurate skeleton or trimethylol) An isocyanate compound represented by), which represents a propane skeleton, etc., can be used alone or in admixture of two or more.

Further, isocyanate compounds represented by the following formulas (a) to (g) can also be used.

[0032]

In order to impart weather resistance to holograms and the like formed using the photocurable resin composition of the present invention, the isocyanate compound is isophorone diisocyanate, hexamethylene diisocyanate, hydrogenated 4,4'-diphenylmethane diisocyanate, Hydrogenated xylylene diisocyanates and the isocyanate compounds of the above formulas (d) to (to) are preferred.

Examples of the compound having 1 to 4 hydroxyl groups include methanol, ethanol, propanol, 1,3-butanediol, 1,4-butanediol, trimethylolpropane, pentaerythritol,
Examples thereof include diglycerol and the like, polyester prepolymer having a hydroxyl group, polyether prepolymer, polycarbonate prepolymer, polybutadiene prepolymer and the like.

The polyester prepolymer having 1 to 4 hydroxyl groups is (i) an addition reaction product of a diol compound having an aromatic or spiro ring skeleton with a lactone compound or its derivative or an epoxy compound, and (ii) a polyaddition product. Examples thereof include a condensation reaction product of a basic acid and a polyol, and (iii) a cyclic ester compound. These may be used alone or in combination of two or more.

Examples of the above-mentioned (i) diol compound having an aromatic or spiro ring skeleton include: Etc. Further, as the lactone compound, for example, ε-caprolactone, δ-valerolactone and the like are representative.

Examples of the polybasic acid used to obtain the condensation reaction product of (ii) above include saturated polybasic acids such as phthalic acid, isophthalic acid, terephthalic acid, adipic acid, succinic acid and sebacic acid. Unsaturated polybasic acids such as acids, maleic acid, fumaric acid, itaconic acid and citraconic acid can be mentioned. Examples of the polyol include ethylene glycol, diethylene glycol, 1,4-butanediol,
1,6-hexane glycol and the like can be mentioned.

Examples of the polyether prepolymer having 1 to 4 hydroxyl groups include polytetramethylene ether glycol, polyethylene glycol, polypropylene glycol and the like. Examples of the polycarbonate having 1 to 4 hydroxyl groups include Praxel CD-210 (molecular weight 1
000), Praxel CD-220 (molecular weight 2000)
And Nippon Polyurethane Industry Co., Ltd. DN-983 (molecular weight 1000). Examples of polybutadiene prepolymers include diols having OH groups at both ends of 1,4- or 1,2-polybutadiene.

In addition to having the above 1-2 hydroxyl groups,
The compound having 5 to 5 acryloyl groups or methacryloyl groups is a radically polymerizable compound that reacts with the isocyanate groups of the isocyanate compound and easily generates radicals by irradiation with ionizing radiation to cause a crosslinking reaction. Such a (meth) acrylate compound having a hydroxyl group is acrylic acid or methacrylic acid, or an ester compound thereof, which is an acrylate or a methacrylate having a hydroxyl group. For example, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, 4-hydroxycyclohexyl acrylate, hydroxybutyl methacrylate, hydroxypropyl methacrylate, 5-
Acrylate or methacrylate having one radical polymerizable unsaturated group such as hydroxycyclooctyl acrylate and 2-hydroxy-3-phenyloxypropyl acrylate, and a compound or penta having two radical polymerizable unsaturated groups represented by the following formula. Examples thereof include erythritol triacrylate and dipentaerythritol pentaacrylate.

[0040]

In the present invention, in addition to the above urethane acrylate, the same isocyanate compound as above and 1
A molecular weight obtained by reacting with an acrylate or a methacrylate having 4 to 4 hydroxyl groups and 1 to 5 acryloyl groups or methacryloyl groups is 500 to 50,000.
The urethane acrylate of can also be used. The urethane acrylate described above is disclosed in JP-A-3-1984.
It can be produced by reacting each of the above components under the reaction conditions described in Method 2.

[0042]

[0043] The amount of the urethane Aku relay bet is,
0.1 per 100 parts by weight of the urethane-modified acrylic resin
To 50 parts by weight, preferably 10 to 30 parts by weight. If it is less than 0.1 parts by weight, the strength, heat resistance, scratch resistance, water resistance, chemical resistance, and adhesion to the substrate of the resulting cured resin layer will not be sufficient, and if it exceeds 50 parts by weight, It is not preferable in that the tack of the surface becomes high to cause blocking, or the plate partially remains on the material at the time of copying (plate is taken).

Further, in order to adjust the flexibility and crosslink density of the resin layer obtained after curing, the photocurable resin composition of the present invention may be added with a conventional thermoplastic resin, acrylic resin, or other monofunctional or polyfunctional resin. Monomers, oligomers and the like can be included. For example, in the case of monofunctional, tetrahydrofurfuryl (meth) acrylate, hydroxyethyl (meth) acrylate, vinylpyrrolidone, (meth) acryloyloxyethyl succinate, (meth) acryloyloxyethyl phthalate, and other mono (meth) acrylates, and bifunctional or higher. Then, when classified by the skeleton structure, polyol (meta)
Acrylate (epoxy modified polyol (meth) acrylates, such as lactone-modified polyol (meth) acrylate), a polyester (meth) acrylate, epoxy (meth) acrylate, Others polybutadiene, isocyanuric acid, hydantoin, melamine, phosphorus It is a poly (meth) acrylate having an acid-based, imide-based, phosphazene-based skeleton, and various monomers, oligomers, and polymers that are curable by ultraviolet rays and electron beams can be used.

More specifically, a bifunctional monomer,
Polyethylene glycol di (meth) as oligomer
Acrylate, polypropylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate and other trifunctional monomers, oligomers and polymers as trimethylolpropane tri (meth) acrylate , Pentaerythritol tri (meth) acrylate,
Examples of tetrafunctional monomers and oligomers such as aliphatic tri (meth) acrylate include pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, and aliphatic tetra (meth) acrylate. monomer, the oligomer dipentaerythritol penta (meth) acrylate, other such dipentaerythritol hexa (meth) acrylate, polyester skeleton, has a full Osufazen skeleton (meth) acrylate. The number of functional groups is not particularly limited, but if the number of functional groups is less than 3, heat resistance tends to decrease, and if it is 20 or more, flexibility tends to decrease. Is preferred.

The amount of the above monomer or oligomer used is in the range of about 5 to 40 parts by weight, preferably about 10 to 30 parts by weight, per 100 parts by weight of the urethane-modified acrylic resin. When the amount of the monomer or oligomer used is less than the above range, the strength of the obtained cured resin layer,
Heat resistance, scratch resistance, water resistance, chemical resistance, adhesion to the substrate is not sufficient, on the other hand, if the amount of the monomer or oligomer used exceeds the above range, the tack of the surface becomes high, causing blocking. In addition, when the hologram or the like is duplicated, a part of the material remains on the printing plate (press stamper) (printing is performed), so that the repetitive embossing property is deteriorated.

In the present invention, when the photocurable resin composition is cured by ultraviolet rays, it is necessary to add a photosensitizer to the composition, while when it is cured by an electron beam. No photosensitizer is required. As the photosensitizer, various photosensitizers used as photosensitizers for conventional UV-curable coating materials, for example, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, α-methylbenzoin. , Benzoin compounds such as α-phenylbenzoin;
Anthraquinone compounds such as anthraquinone and methylanthraquinone; benzyl: diacetyl; phenylketone compounds such as acetophenone and benzophenone; sulfide compounds such as diphenyldisulfide and tetramethylthiuram sulfide; α-chloromethylnaphthalene; anthracene and hexachlorobutadiene, pentachlorobutadiene and the like And the like. Such a photosensitizer is the urethane-modified acrylic resin 1 described above.
It is preferably used in the range of about 0.5 to 10 parts by weight per 00 parts by weight.

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

Next, the use of the photocurable resin composition of the present invention will be described with reference to some examples. A temperature at which the photocurable composition is applied or impregnated on a substrate such as a metal plate, paper, or polyethylene terephthalate, and then the organic solvent contained in the composition is scattered, for example, 100 to 165 ° C.
The photocurable resin layer is formed on the base material by introducing the film into the heating furnace set for 1 to about 0.1 to 1 minute and drying it. Then, a desired hologram relief patterning (embossing) is performed on the photocurable resin layer using, for example, a press stamper, and then the resin layer is photocured by irradiation with ultraviolet rays, electron beams or the like.

Since the obtained hologram is generally a transmission type, it is necessary to provide a reflection layer. If a metal thin film that reflects light is used as the reflective layer, it becomes an opaque type hologram, and if it is a transparent substance and has a refractive index difference from that of the hologram layer, it becomes a transparent type, but both can be used in the present invention. The reflective layer is sublimation, vacuum deposition, sputtering,
It can be formed by a known method such as reactive sputtering, ion plating, or electroplating.

Examples of the metal thin film for forming the opaque type hologram include Cr, Ti, Fe, Co and N.
i, Cu, Ag, Au, Ge, Al, Mg, Sb, P
b, Pd, Cd, Bi, Sn, Se, In, Ga, Rb
It is a thin film formed of a single metal or a combination of two or more of such metals and oxides and nitrides thereof. Among the above metal thin films, Al, Cr, Ni, Ag, Au and the like are particularly preferable, and the film thickness thereof is 1 to 10,000 nm, preferably 2
It is in the range of 0 to 200 nm.

The thin film forming the transparent type hologram may be made of any material as long as it is light-transmissive and capable of exhibiting the hologram effect. For example, there is a transparent material having a refractive index different from that of 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 refractive index is preferably 0.1 or more, more preferably 0.5.
It is above, 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 a transparent type reflective layer that is preferably used, titanium oxide (Ti
O ₂ ), zinc sulfide (ZnS), Cu / Al mixed metal oxide, and the like.

More specifically, the hologram pattern is embossed by a usual method, for example, using a pair of embossing rolls consisting of a metal roll having a press stamper mounted on its peripheral surface and a paper roll. , 50-15
It is carried out at 0 ° C. and a pressure of 10 to 50 kg / cm ² . One-sided embossing is sufficient for embossing, but double-sided embossing is also possible. When embossing, it is important to set the temperature of the embossing roll, and 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 sticking to the embossed plate, the relationship is completely opposite. In consideration of the effective heat capacity, the transfer speed of the film to be reproduced is also important. In order to reduce the adhesion of the resin composition to the embossing roll, selection of the above-mentioned mold release agent is also important.

Further, by using the photocurable resin composition of the present invention, the photocurable resin composition is applied to the surface of a substrate that has been offset printed in advance, and after drying, the photocurable resin is embossed. It can be photocured to form a relief to produce a three-dimensional map or poster. Furthermore,
First release film made of polyethylene terephthalate
After coating the photocurable resin composition on the base material of No. 1, dried, printing a pattern on the photocurable resin layer, then applying a hot stamping agent on the printed surface, plywood, ABS sheet, zinc plate A second base material such as the above is attached to the hot stamping agent surface, the resin layer printed on the second base material is transferred by a heat transfer roll or the like, the release film is removed, and the exposed photocurable resin layer is exposed. By photocuring the film, a film, a metal plate or the like having a pattern transferred to a substrate can be manufactured.

Light used for curing the photocurable resin composition of the present invention includes high energy ionizing radiation and ultraviolet rays. As the high-energy ionizing radiation source, for example, an electron beam accelerated by an accelerator such as Cockcroft accelerator, Handegraaf accelerator, linear accelerator, betatron, cyclotron is industrially most convenient and economically used. However, radiation such as γ-rays, X-rays, α-rays, neutron rays, and proton rays emitted from radioactive isotopes and nuclear reactors can also be used. Examples of the ultraviolet ray 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 solar lamp.

[0056]

EXAMPLES Next, the present invention will be described more specifically with reference to Examples and Comparative Examples. In addition, parts or% in the examples are based on weight unless otherwise specified. Example 1 The following six types of photocurable resin compositions A to F of the present invention were prepared using the resin solutions obtained in the above Production Examples 1 to 6. Composition A : Resin solution of Production Example 1 (based on solid content) 100 parts Silicone: trimethylsiloxysilicic acid-containing methylpolysiloxane (trade name KF-7312, manufactured by Shin-Etsu Chemical Co., Ltd.) 1 part Urethane acrylate (trade name Shiko UV- 1700B, manufactured by Nippon Gohsei Co., Ltd. 10 parts Polyfunctional monomer (trade name SR-399, manufactured by Sartomer) 10 parts Photosensitizer (trade name Irgacure 907, manufactured by Ciba Specialty Chemicals) 5 parts Diluted with methyl ethyl ketone (MEK) The solid content of the composition was adjusted to 50%.

Composition B : Resin solution of Production Example 2 (based on solid content) 100 parts Silicone: Amino-modified reactive silicone oil (both ends type) (trade name KF-8012, manufactured by Shin-Etsu Chemical Co., Ltd.) 1 part Urethane acrylate (Brand name Shikotsu UV-3000B, manufactured by Nippon Synthetic Chemical Industry) 15 parts Polyfunctional monomer (Brand name SR-399, manufactured by Sartomer) 10 parts Photosensitizer (Brand name IRGACURE 651, manufactured by Ciba Specialty Chemicals) 5 parts Methyl ethyl ketone The solid content of the composition was adjusted to 50% by diluting with (MEK).

Composition C : Resin solution of Production Example 3 (based on solid content) 100 parts Silicone oil: Amino-modified reactive silicone oil (side chain type) (trade name KF-860, manufactured by Shin-Etsu Chemical Co., Ltd.) 1 part Urethane Acrylate (trade name: SHIKO UV-3200B, manufactured by Nippon Synthetic Chemical Industry) 15 parts Polyfunctional monomer (trade name: NK Oligo U-15HA, manufactured by Shin Nakamura Chemical Co., Ltd.) 5 parts Photosensitizer (trade name: IRGACURE 907, Ciba Specialty Chemicals) The product was diluted with 5 parts methyl ethyl ketone (MEK) to adjust the solid content of the composition to 50%.

Composition D : Resin solution of Production Example 4 (based on solid content) 100 parts Silicone oil: Amino-modified reactive silicone oil (one end type) (trade name KF-8012, manufactured by Shin-Etsu Chemical Co., Ltd.) 1 part Urethane Acrylate (trade name: SHIKO UV-7500B, manufactured by Nippon Synthetic Chemical Industry) 20 parts Polyfunctional monomer (trade name: SR-399, manufactured by Sartomer) 5 parts Photosensitizer (trade name: IRGACURE 907, manufactured by Ciba Specialty Chemicals) 5 parts The solid content of the composition was adjusted to 50% by diluting with methyl ethyl ketone (MEK).

Composition E : Resin solution of Production Example 5 (based on solid content) 100 parts Silicone: Methacryl modified silicone oil (trade name X-22-164B, manufactured by Shin-Etsu Chemical Co., Ltd.) 3 parts Urethane acrylate (trade name Shiko UV) -3000B, manufactured by Nippon Gohsei Co., Ltd. 15 parts Photosensitizer (trade name Irgacure 651, manufactured by Ciba Specialty Chemicals) 5 parts Diluted with methyl ethyl ketone (MEK) to adjust the solid content of the composition to 50%.

[0061]

(1) Duplication of Hologram Duplication of a hologram was performed by the continuous duplication device shown in FIG. 1 described in JP-A No. 61-156273. Each of Examples 2-6 above 5 kinds of photocurable resin composition of the present invention 5
20 m / min. On the easy-adhesion-treated surface of a polyethylene terephthalate film (Diafoil T-600E, manufactured by Diafoil Hoechst Co., Ltd.) having a single-sided easy adhesion treatment of 0 μm. After coating with a roll coater at 100 ° C. and drying at 100 ° C. to volatilize the solvent, a photosensitive film for duplication having a dry film thickness of 2 g / m ² was obtained. All the obtained films were not sticky at room temperature and could be stored in a wound state.

The embossing roller of the copying apparatus is provided with a press stamper which is subsequently created from a master hologram created by using a laser beam. A replica hologram prepared from a master hologram on a resin plate and attached on a cylinder can also be used. Mount the photopolymer film for reproduction prepared above on the paper feed side, and
A hot press was applied at 50 ° C. to form a fine uneven pattern. Subsequently, it was photo-cured by irradiating it with ultraviolet rays generated from a mercury lamp. Subsequently, an aluminum layer was vapor-deposited thereon by a vacuum vapor deposition method to form a reflection type relief hologram.

On this surface, an adhesive layer (Nisetsu PE-1
18 + CK101, manufactured by Nippon Carbide Co., Ltd., is applied by a roll coat, dried at 100 ° C. to evaporate the solvent, and then a silicone-treated PET film (SP) is used as a release film.
O5, manufactured by Tokyo Cellophane Paper Co., Ltd.) was laminated to obtain an adhesive layer having a dry film thickness of 25 g / m ² . This is in the form of a label and can be used for a printed matter, a display, or the like that displays a stereoscopic image.

(2) Forming Diffraction Grating FIG.
No. 156273). Each of Example 7-1 1 the five photo-curable resin composition of the present invention 5
20 m / min. On the easy-adhesion-treated surface of a polyethylene terephthalate film (Diafoil T-600E, manufactured by Diafoil Hoechst Co., Ltd.) having a single-sided easy adhesion treatment of 0 μm. After coating with a roll coater at 100 ° C. and drying at 100 ° C. to volatilize the solvent, a photosensitive film for duplication having a dry film thickness of 2 g / m ² was obtained. All the obtained films were not sticky at room temperature and could be stored in a wound state.

The embossing roller of the copying apparatus is provided with a press stamper which is subsequently created from a master diffraction grating drawn by using an electron beam. It is also possible to use a resin plate in which a duplicated diffraction grating is prepared from the master diffraction grating and is stuck on a cylinder. The duplicating photosensitive film prepared above was set on the paper feed side and heated and pressed at 150 ° C. to form a fine uneven pattern. Subsequently, it was photo-cured by irradiating it with ultraviolet rays generated from a mercury lamp. Subsequently, an aluminum layer was vapor-deposited thereon by a vacuum vapor deposition method to form a reflection type diffraction grating.

On this surface, an adhesive layer (Nissetsu PE-1
18 + CK101, manufactured by Nippon Carbide Co., Ltd., is applied by a roll coat, dried at 100 ° C. to evaporate the solvent, and then a silicone-treated PET film (SP) is used as a release film.
O5, manufactured by Tokyo Cellophane Paper Co., Ltd.) was laminated to obtain an adhesive layer having a dry film thickness of 25 g / m ² . This is in the form of a label and can be used for a printed matter, a display, or the like that displays a stereoscopic image.

(3) Hologram formation by transfer method Example 12 A polyethylene terephthalate film (Lumirror T60, manufactured by Toray Industries, Inc.) having a thickness of 2 to 16 25 μm was applied at 20 m / min. The peeling layer is coated with a gravure coat at a speed of 1 and dried at 100 ° C. to volatilize the solvent, and then the peeled layer / P of the dried film thickness is 1 g / m ^2.
A film having a layer structure of ET was obtained.

The peeling layer in the above is a layer which is transferred to the surface of the transferred material and becomes the outermost surface after transferring the transfer foil, and is provided for the purpose of improving the peeling property and the foil cutting property of the transfer layer. However, various known materials can be used depending on the type of the base film. Examples of the material of the release layer include one or more of polymethacrylic acid ester resin, polyvinyl chloride resin, cellulose resin, silicone resin, chlorinated rubber, casein, various surfactants, metal oxides, and the like. A mixture is used. In particular, the peeling layer has a peeling force between the base film and the transfer layer of 1 to 5 g / inch (90
It is preferable that the material and the like be appropriately selected so as to form (peeling). This release layer can be formed into an ink and formed on the surface of the base film by a known method such as coating, and its thickness is 0.
The range of 1 to 2 μm is preferable.

Each of the above-mentioned five photocurable resin compositions of the present invention was coated on a release layer of a film having a layer structure of release layer / PET with a roll coater and dried at 100 ° C. to evaporate the solvent. After that, a photosensitive film for duplication having a dry film thickness of 2 g / m ² was obtained. All the obtained films were not sticky at room temperature and could be stored in a wound state.

The embossing roller of the copying apparatus is provided with a press stamper which is subsequently created from a master hologram created using laser light. A replica hologram prepared from a master hologram on a resin plate and attached on a cylinder can also be used. Mount the photopolymer film for reproduction prepared above on the paper feed side, and
A hot press was applied at 50 ° C. to form a fine uneven pattern. Subsequently, it was photo-cured by irradiating it with ultraviolet rays generated from a mercury lamp. Subsequently, an aluminum layer was vapor-deposited thereon by a vacuum vapor deposition method to form a reflection type relief hologram. An adhesive layer was applied to this surface by gravure coating, dried at 100 ° C. to volatilize the solvent, and an adhesive layer having a dry film thickness of 1 g / m ² was obtained.

As the above-mentioned adhesive layer, a known heat-sensitive adhesive resin can be used. For example,
Rubber-based materials such as polyisoprene rubber, polyisobutylene rubber, and styrene-butadiene rubber, methyl poly (meth) acrylate, ethyl poly (meth) acrylate, propyl poly (meth) acrylate, butyl poly (meth) acrylate, poly ( (Meth) acrylic ester such as 2-ethylhexyl acrylate, polyvinyl ether such as polyisobutyl ether, polyvinyl acetate such as polyvinyl acetate, vinyl chloride-vinyl acetate copolymer, polyacrylamide, polymethylolacrylamide Polyamide series such as, polyvinyl chloride series such as polyvinyl chloride, polystyrene,
Polyester, polychlorinated olefins, polyvinyl butyral, and others, vinyl acetate / octyl acrylate,
Examples thereof include vinyl acetate / butyl acrylate and vinylidene chloride / butyl acrylate.

The film to be applied may be any film having transferability and releasability. For example, a biaxially stretched polyethylene terephthalate (PET) film has good dimensional stability, heat resistance and toughness. Most preferred from the point.
In addition to this, polyvinyl chloride film, polypropylene film, polyethylene film, polycarbonate film, cellophane, polyvinyl alcohol film,
Acetate film, nylon film, polyamide film, polyamideimide film, ethylene / vinyl alcohol copolymer film, fluorine-containing film, various coextrusion films and the like can be used. 5μ as thickness
m to 200 μm, preferably 10 μm to 50 μm.

Thermal transfer was performed on the plywood from the film side with the acrylic adhesive side facing down by a heat roll.
Then, the peeling film was peeled off, and ultraviolet rays generated from a mercury lamp were irradiated to cure the resin on the surface layer. This is in the form of a transfer foil, and can be used for a printed matter, a display, or the like showing a stereoscopic image. When thermal transfer was performed on a vinyl chloride card with a transfer machine, the foil was cut well and the adhesion was excellent. Table 2 shows the physical properties of the processed products of Examples 2 to 16 described above.

Comparative Example 1 The same amount of resin (methacrylic acid-acrylic acid copolymer resin BR-77, manufactured by Mitsubishi Rayon Co., Ltd.) was used in place of the resin of the composition A in Example 1, except that silicon oil was not used. A composition G having the same composition as the composition A was prepared, and the composition G was used to perform hologram duplication, diffraction grating duplication, and hologram formation by a transfer method in the same manner as described above. Table 2 shows the physical properties of these processed products.

The evaluation method of the physical properties is as follows. Peelability (Peelability from press stamper) : The coating film is continuously duplicated for 1000 m by the duplicating apparatus shown in FIG. 1 (JP-A 61-156273), and it is confirmed whether or not the resin remains on the press stamper. I went by. ○: There is no remaining. ×: There is a rest. Chemical resistance : When the cured surface of the processed product was rubbed 100 times with a gauze impregnated with methyl ethyl ketone and rubbed, there was no abnormality on the surface, and those with an abnormality on the surface were regarded as defective. ○: Good. X: defective.

Scratch resistance : When the cured surface of the processed product was rubbed 10 times with # 0000 steel wool, the surface without any change was evaluated as good, and the surface scratched and whitened as defective. ○: Good. X: defective. Evaporation suitability : After depositing an aluminum layer on the hologram or diffraction grating formation surface by a vacuum evaporation method, the adhesion was evaluated by a cellotape cross-cut test. ◎ ・ ・ ・ Very good vapor deposition. Good: Good vapor deposition property.
X: Poor vapor deposition property. ○: Good. X: defective. Bending resistance : The transfer foil transferred onto a polyvinyl chloride card was subjected to embossed character processing, and it was confirmed whether the embossed character had cracks or the like. ○: No change. X: There is a crack.

[0078]

[0079]

According to the present invention, by using a specific urethane-modified acrylic resin as a main film forming component of a photocurable resin composition, excellent strength, heat resistance, scratch resistance, water resistance, It is possible to form a film with excellent chemical resistance, adhesion to the substrate, and especially metal vapor deposition on the surface,
Further, it is possible to provide a photocurable resin composition capable of forming a diffraction grating or a relief hologram which also has flexibility and flexibility to follow the adherend.

[Brief description of drawings]

FIG. 1 is a diagram for explaining a method of giving an uneven shape used in the present invention.

─────────────────────────────────────────────────── ─── Continuation of the front page (58) Fields surveyed (Int.Cl. ⁷ , DB name) C08L 33/06-33/16 C08L 75/04-75/16 G02B 5/18 G03H 1/04

Claims (10)

(57) [Claims] 1. A urethane-modified acrylic resin represented by the following structural formula, a release agent, and urethane acrylate are contained as essential components, and the urethane acrylate contains two or more units.
An isocyanate compound having an isocyanate group and 1 to
A urethane acrylate having a molecular weight of 500 to 50,000 obtained by reacting with an acrylate or methacrylate having four hydroxyl groups and one to five acryloyl groups or methacryloyl groups, or an isocyanate compound having two or more isocyanate groups. , A urethane acrylate having a molecular weight of 500 to 50,000 obtained by reacting a compound having 1 to 4 hydroxyl groups with a compound having 1 to 2 hydroxyl groups and 1 to 5 acryloyl groups or methacryloyl groups. A photocurable resin composition comprising: (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 are linear or branched. Represents an alkylene group, where the sum of l (el), m, n, and o (o) is 100.
In this case, l is 20 to 90, m is 0 to 50, and n is 1.
0 to 80 and o are integers of 0 to 20. ) 2. The photocurable resin composition according to claim 1, wherein the release agent is contained in an amount 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. A urethane acrylated bets is the resin 10
The photocurable resin composition according to claim 1, which is contained in an amount of 0.1 to 50 parts by weight per 0 parts by weight. 6. The photocurable resin composition according to claim 1, wherein the resin has a molecular weight of 10,000 to 200,000. 7. The photocurable resin composition according to claim 1, which contains a polyfunctional monomer or a polyfunctional oligomer. 8. The photocurable resin composition according to claim 1 is applied and dried on at least one surface of a substrate to form a photocurable resin layer, A method for forming a concavo-convex pattern, comprising embossing the surface of a curable resin layer and then exposing the resin layer to cure the resin layer. 9. The method for forming a concavo-convex pattern according to claim 8, wherein the exposure is performed with ultraviolet rays or electron beams. 10. The method for forming an uneven pattern according to claim 8, wherein the uneven pattern is a diffraction grating or a relief hologram.