KR100955912B1 - Photopolymer composition and law shrinkage photopolymer film prepared therefrom - Google Patents

Abstract

The present invention provides an ad molecule composition for preparing a low shrinkage ad molecule film comprising 1) 5 to 60% by weight of a photopolymerizable monomer, 2) 30 to 90% by weight of a binder, and 3) 0.001 to 10% by weight of an initiator; Method for producing an advertising molecule film using the composition; And an optical recording medium comprising such a film.

Using the advertising molecule composition according to the present invention can have a high transmittance and low shrinkage rate to produce a hologram storage advertising molecule film with high stability after hologram recording.

Photopolymerizable composition, advertising molecule film, holography, 3D optical recording medium

Description

Ad-molecule composition and low-shrinkable ad-molecule film prepared therefrom {PHOTOPOLYMER COMPOSITION AND LAW SHRINKAGE PHOTOPOLYMER FILM PREPARED THEREFROM}

The present invention relates to an advertising molecule composition for producing a low-shrinkable advertising molecule film and a hologram recording medium produced using the composition.

The advertising molecule is a photopolymerizable organic polymer material, which is easy to process, inexpensive, and has high sensitivity to light. Ad molecules that react with the mechanism of polymerization difference according to the intensity of light generated by the interference of light are generally composed of acrylic monomers, epoxy monomers, initiators, and polymer binders. Advertisement molecules, unlike previous photo plates, are self-developing and fixing without a wet process, are simple to produce, and have the same thickness. Since it has a characteristic of more than 2500 times diffraction efficiency, it can be applied as a holographic recording material of WORM (Write Once Read Many) type and also as a security medium through hologram recording. Recently, researches for application to 3D bit memory using hologram recording have begun, and holograms are used as security elements in security-required currencies such as securities and identification cards.

Such advertising molecules have high applicability as holographic media, and research on security films using holograms has been made. Advertising molecule recording media using photopolymerizable monomers have a problem that information is changed after recording due to the polymerization of monomers during hologram recording. [Optical Materials, Volume 30, Issue 4, December 2007, Pages 662-668] As a holographic medium, a photopolymerizable monomer is an acrylic monomer which is more reactive than an epoxy. Mater. 30 (2007) 637-644], epoxy-based monomers have been studied because of the high shrinkage and the problem of deformation after polymerization [SPIE Vol. 6488, 648806, (2007.02).

It is an object of the present invention to provide an advertising molecule composition and a low-shrinkable advertising molecule film prepared using the same, which solves the problems of the existing inventions such as high shrinkage of the photopolymerizable monomer.

The inventors of the present invention prepare an advertising molecule film using an advertising molecule composition comprising an epoxy group and a photopolymerizable monomer having an acrylic group (or methacryl group) similar structure in one molecule at the same time. The present invention has been found to have a high light transmittance as well as a low shrinkage ratio and to complete the present invention.

When the photopolymerizable polymer composition according to the present invention is used, a light transmittance and a low shrinkage rate may produce a hologram storage advertisement molecule film having high stability after hologram recording. In addition, since the composition of the present invention uses a photopolymerizable monomer synthesized through a simple synthesis process from an inexpensive initial material, not only has a high commercial competitiveness in terms of price, but also an advertising molecule film prepared therefrom does not cause an irritating odor and commercializes. When you have the advantage that does not give inconvenience.

The present invention provides an advertising molecule composition for producing a low-shrinkable advertising molecule film comprising the composition as follows.

1) 5 to 60% by weight photopolymerizable monomer;

2) 30 to 90 wt% binder; And

3) 0.001 to 10 wt% of initiator

The photopolymerizable monomer used in the advertising molecule composition of the present invention is at least one compound represented by the following formula (1).

[Formula 1]

In the above formula,

X is selected from substituted or unsubstituted alkylene, arylene, arylalkyl, bisphenylalkyl, bisphenylsulphone, bisphenylsulfur, or bisphenyloxy having 1 to 20 carbon atoms,

Y is a linking group or is selected from oxy alkylene, thioalkylene, or O, S, N,

Z may be hydrogen or a methyl group,

a and b are integers of 1 or 2.

As a specific example, the compounds of formula 1 that can be used in the present invention include the following.

[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

[Formula 1-5]

[Formula 1-6]

[Formula 1-7]

[Formula 1-8]

[Formula 1-9]

[Formula 1-10]

[Formula 1-11]

Such monomers are preferably included in the range of 5 to 60% by weight in the composition.

 When the content range of the monomer is less than 5% by weight, there is a problem that the hologram is not recorded, and when the content range exceeds 60% by weight, there is a disadvantage in that a film is not formed.

The binder used in the advertising molecule composition of the present invention serves to bind each component contained in the composition, and any transparent polymer or organic or inorganic hybrid type polymer commonly used as a binder in the art may be used. In particular, one or more polymers selected from the group consisting of polysulfone, polymethyl methacrylate (PMMA), polystyrene methacrylate copolymer, aromatic polyester, and the like can be used.

The binder is preferably included in the range of 30 to 90% by weight in the composition. This is because when the content of the binder is less than 30% by weight, the components cannot be combined properly, and when the content of the binder is more than 90% by weight, holography is not recorded.

The initiator used in the advertising molecule composition of the present invention is at least one compound selected from all initiators used in conventional polymerization. Both cationic photoinitiators and radical photoinitiators may be used, specifically, Union Carbide's Cyracure UVI-6990, Cyracure UVI-6974; Degacure of Degusa; Asahi Denka's SP-55, SP-150, SP-170; Irgacure 261, Irgacure 184, Irgacure 819, Irgacure 907, Irgacure 2959 by Ciba-Geigy; As a pulluka product, it may be at least one selected from Darocure 1173, Darocure 4265, Darocure 1664 and the like.

 The initiator is preferably included in 0.001 to 10% by weight in the composition. This is because when the content of the initiator is less than 0.001% by weight, sufficient and proper polymerization initiation does not occur, and when it exceeds 10% by weight, holographic recording does not occur.

In addition, the advertising molecule composition of the present invention may further contain an organic solvent for dissolving the solid components in the monomer, initiator, and binder in an amount of 5 to 99 parts by weight based on 100 parts by weight of the composition containing the components 1) to 3). Can be. The organic solvent is one or more selected from the group consisting of chloroform, tetrachloromethane and tetrachloroethane; In addition, methanol, ethanol, isopropanol, n-butanol, methylisocarbinol, acetone, 2-butanone, ethyl amyl ketone, diacetone alcohols, iso Isophorone, cyclohexanone, NN-dimethylformamide, N, N-dimethylacetoamide, diethyl ether, diethyl ether Isopropyl ether, tetrahydrofuran, 1,4-dioxane, 3,4-dihydro-2H-pyran, 3,4-dihydro-2H-pyran, 2-methoxy ethanol, 2-ethoxy ethanol, 2-butoxy ethanol, ethylene glycol dimethyl ether, methyl acetate methyl acetate, ethyl acetate, isobutyl acetate, amyl acetate, Lactate (ethyl lactate), ethylene carbonate (ethylene carbonate); Aromatic hydrocarbons such as benzene, toluene, xylene, hexane, peptane, iso-octane, cyclohexane, methylene chloride, 1,2-dichloroethane, dichloropropane, chlorobenzene , From the group consisting of dimethylsulfoxide, N-methyl-2-pyrrolidone, and N-octyl-2-pyrrolido ne One or more selected species can be mixed and used.

In order to improve the polymerization rate and efficiency, the monomers including unsaturated groups such as vinyl, acrylic, and methacryl groups may be added to the ad molecule composition of the present application. Specifically, the following compounds can be used.

CH ₂ = CH-C (= O) SCH ₂ CH ₂ SCH ₂ CH ₂ SC (= O) -CH = CH _{2 ,}

The monomer containing such an unsaturated group is used in the range of 1 to 200 weight ratio with respect to 1 weight of the photopolymerization monomer of Chemical Formula 1, and when the usage amount is less than 1 weight ratio, the effect is not expressed. It is desirable to maintain this range because poor problems occur.

In order to improve the processability or physical properties of the coating film, a polymer polymer resin may be used in the advertising molecule composition of the present application. Butyral, polyolefin, polyvinyl chloride resins, polyvinyl acetate resins, vinyl chloride-vinyl acetate copolymers, polystyrene resins, stylene Styrene copolymers, phenoxy resins, polyester resins, aromatic polyester resins, polyurethane resins, polycarbonate resins, poly Acrylate resins, polymethacrylates Polymethacrylate resins, acrylic copolymers, maleic anhydride copolymers, polyvinyl alcohol resins, modified polyvinyl alcohol resins, hydroethyl cellulose Hydroxyethyl cellulose resins, carboxymethyl cellulose resins, starches or mixtures thereof may be used.

Such polymer polymer resin may be used in the range of 1 to 500 parts by weight based on 100 parts by weight of the advertising molecule composition. If the amount is less than 1 part by weight, it is difficult to express the desired physical properties. It is desirable to maintain this range because loss occurs.

 In addition, a photo sensitizer may be mixed with the advertisement molecule composition of the present invention in order to promote photopolymerization or to react in a wavelength band capable of holographic optical recording. As a photosensitizer, at least one compound selected from anthracene, perylene, methyl red, methyl orange, methylene blue, pyran derivatives, acridine compounds, mono-, di- or tri-halomethyl-substituted triazines and quinazolinones Can be used.

Such a photosensitizer is used in the range of 0.01 to 20% by weight with respect to the curable photopolymerized composition. When the amount is less than 0.01% by weight, the sensitizing effect is poor, and when the amount exceeds 20% by weight, a polymer having a low molecular weight is produced. It is preferable to maintain the above range because is generated.

In addition, the composition of the present invention may be expanded as needed; Layered silicates; Nano powder; Liquid crystals; Other dyes; Various additives such as antioxidants, dyes, pigments, lubricants, thickeners and the like for improving heat resistance, mechanical properties, processing properties and the like; Or fillers. It may also include a polymerization catalyst for promoting the polymerization reaction, a UV absorber for improving weather resistance, or a colorant.

It is preferable to mix and use these components in an appropriate amount within the range which does not deviate from the objective of this invention.

The advertising molecule composition according to the present invention is a composition in which polymerization occurs by light, and has excellent photopolymerization efficiency, such as optical coating, imaging, optical disc, optical head, holography media, optical recording, electrode, optical switch, display element and / or sensor, It can be effectively applied to security film coating of securities.

In another aspect, the present invention, the step of coating the advertising molecule composition according to the invention on a substrate, and drying in a temperature of -20 ℃ to 300 ℃, preferably room temperature to 130 ℃ to form an advertising molecule film on the surface of the substrate It provides an advertising molecule film manufacturing method comprising a. The substrate is an object to which the advertising molecule composition is coated, and may be, for example, a silicon wafer, a glass substrate, a plastic film, quartz, fiber, paper, wood, or the like.

 The method of coating the advertising molecule composition on the substrate may be any method as long as it is commonly used in the art, but preferably a solution coating method, for example, spin coating, flow coating, bar coating, screen coating, spray coating, or the like. It is better to use the method.

It is preferable that the thickness of the advertising molecule film formed is 0.01 micrometer or more. This is because a problem of low recording density occurs when the thickness of the film is less than 0.01 mu m.

As another application method of the advertising molecule composition for hologram storage according to the present invention, the present invention is filled in the mold for producing a molded article and dried at a temperature of about 130 ℃ or less, preferably room temperature to 130 ℃ To provide a method comprising the step of producing a final advertising molecule film.

In still another aspect, the present invention provides an organic semiconductor, an optical recording medium, a display device, a recording device, a lens, an anti-counterfeiting film or a coating, a color changeable fiber, a color changeable container, or a medicine to which the advertisement molecule composition according to the present invention is applied. Providing products for various purposes. The product to which the composition according to the present invention is applied may be an optical recording product such as an optical disk, an optical recording film, an optical coating liquid, an optical head, a holographic media, an electrode, an optical switch, an optical display device and / or an optical sensor. The product has the advantage that the shrinkage rate after the hologram recording and high light transmittance by applying the advertising molecule composition according to the present invention.

Hereinafter, the present invention will be described in detail through examples. However, the following examples are only for illustrating the present invention specifically, and the scope of the present invention is not limited by these examples.

Example

material

Compounds of formula (I) used in the following examples were synthesized according to the articles of the Journal of Organic Chemistry of the USSR, 11, 8, 1616, (1974), and the reagents used in the following examples are not specifically mentioned. It was purchased from Aldrich (USA), TCI (Japan), Merck [Germany] or synthesized by a known method. The solvent used in the reaction was purchased from Aldrich (USA) or Deoksan Chemical in Korea.

Experimental Example Property measurement

The photosensitive properties of the compositions prepared in Examples and Comparative Examples and the diffraction efficiency, light transmittance, and shrinkage, which are physical properties of the advertising molecular film, were measured by the following method.

(1) Photosensitive characteristics

After coating the advertising molecule composition on a slide substrate, the absorbance at 200 ~ 900 nm was measured by using a UV spectrometer to measure the absorption wavelength region of 0.2 or more absorbance.

(2) Diffraction efficiency (%)

The holographic properties of the advertising molecule film were measured as follows. A diode laser (491 nm) was used as a recording source, and the plane wave was used by controlling the polarization with a polarizer and using a spatial filter. The intensity ratio of the reference light to the object light was 1: 1, and the hologram was recorded by irradiating the sample at an incident angle of 15 ° with respect to the surface normal of the thin film. Then, the recorded image was read by exposing the hologram to the reference light alone. The diffraction efficiency was calculated by the following equation.

Diffraction efficiency = 100 × (intensity of diffracted light) / (intensity of transmitted light + intensity of diffracted light)

(3) light transmittance ( Transparency ) Measure

The light transmittance of the advertising molecular film was measured at 700 nm using a UV spectrometer.

(4) shrinkage ( Shrinkage ) Measure

 Using a thin film thickness meter, the thickness of the advertising molecule film before and after recording was measured and measured.

Shrinkage = (Reduced thickness after recording / Thin film thickness before recording) X 100

Example  One

0.66 g of the compound having the structure of Formula 1-1, 1 g of polysulfone (molecular weight 35000) and 0.01 g of Cyracure UVI 6974 (manufactured by Union Carbide) were dissolved in a mixed solvent of 2 g of chloroform and 0.5 g of tetrachloroethane. , And stirred for 1 hour at 20 ℃ to prepare an advertising molecule composition.

The ad molecule was coated on a slide glass, dried at room temperature for 10 hours, and dried for 2 hours in a vacuum oven. The absorption wavelength was measured by UV-VIs spectroscopy, and the light sensitivity was observed in 300-360 nm in the ultraviolet region and 480-520 nm in the visible region. I could see that.

Example  2-10 and Comparative example

The composition of Example 1 was changed as shown in Table 1, and the experiment of the same process was repeated. Each composition was prepared by stirring for 2 hours in a nitrogen atmosphere at 30 ℃, and then coated on a slide glass to measure the photosensitive area.

Example  Ingredients (wt%)  Photosensitive area Monomer bookbinder Initiator Other additives (nm)  2 1-1 (20) 1-2 (20) Polysulfone Mn = 50,000 (20) Polyimide Mn = 30,000 (23) Igacure784 (1) Cyracure UVI 6974 (1) Chloroform (10) Dichloromethane (5) 350-400 410-520  3 1-1 (20) 1-4 (20) Polysulfone Mn = 50,000 (20) Polyimide Mn = 30,000 (23) Igacure 784 (1) Cyracure UVI 6974 (1) Chloroform (10) Dichloromethane (5) 350-400 420-600  4 1-2 (20) 1-4 (20) Polysulfone Mn = 50,000 (20) Polyvinyl Alcohol Mn = 50,000 (23) Igacure784 (1) Cyracure UVI 6990 (1) Chloroform (10) Dichloromethane (5) 320-420 420-520  5 1-3 (20) 1-5 (20) Polysulfone Mn = 50,000 (20) Polyvinyl Alcohol Mn = 50,000 (23) Igacure 907 (1) Cyracure UVI 6974 (1) Chloroform (10) Dichloromethane (5) 350-400 440-530  6 1-1 (20) 1-6 (20) Polysulfone Mn = 50,000 (20) Polyvinyl Alcohol Mn = 50,000 (23) Igacure907 (1) Cyracure UVI 6990 (1) Chloroform (10) Dichloromethane (5) 320-420 440-530  7 1-7 (20) 1-8 (20) Polysulfone Mn = 50,000 (20) Polyimide Mn = 30,000 (23) Igacure184 (2) Darocure 1664 (0.5) Chloroform (5) Dimethylformamide (7) 300-400 420-550  8 1-8 (20) 1-9 (20) Polysulfone Mn = 50,000 (20) Polyvinyl Alcohol Mn = 50,000 (23) Igacure784 (1) Darocure 1664 (1) Chloroform (10) Dichloromethane (5) 300-400 420-620  9 1-9 (20) 1-10 (20) Polystyrene-methylmethacrylate Copolymer Mn = 50,000 (43) Igacure784 (1) Cyracure UVI 6974 (1) Chloroform (10) Dichloromethane (5)  350-650  10 1-10 (20) 1-11 (20) Polysulfone Mn = 50,000 (43) Igacure784 (1) Cyracure UVI 6974 (1) Chloroform (10) Dichloromethane (5) 350-400 420-520 Comparative example Acrylamide (40) Polyvinyl Alcohol (57) Triethylamine (2) Photosensitizers-Eosin (1)  490-520

Experimental Example  One

The composition of Example 1 was applied to a glass substrate while rotating at 200 rpm using a spin coater. Then, the glass to which the composition was applied was dried in an oven at 40 ° C. for OV-11 for 3 hours and further dried at 60 ° C. for 2 hours to form an advertising molecule film on the surface of the glass substrate.

 As a result, an advertising molecular film having a thickness of 50 μm could be produced. The prepared film had a transmittance of 95% and a shrinkage rate of 0.1% due to light irradiation at a 491 nm wavelength.

In addition, when recording by the holography method using a 491nm laser, it was confirmed that the interference fringe is recorded as shown in FIG. It was. (See Figure 3)

In the holographic recording part, no phase separation phenomenon occurred even after one year (see FIG. 4), and the diffraction phenomenon and the recording part were maintained, and the recording stability was more than 365 days.

Experimental Example 2-10 and Comparative Experimental Example

In Experimental Example 1, the composition and the film production conditions were changed as shown in Table 2, thereby preparing a low-shrinkable, stable ad molecule film capable of recording in the UV and visible region. The film was coated using bar coating and the substrate was quartz. The film was prepared by drying in air at 30 ° C. for 5 hours, 5 hours in a 50 ° C. nitrogen atmosphere, and 3 hours in a 60 ° C. nitrogen atmosphere.

Composition Film thickness (mm) Transmittance (%) Shrinkage (%) Experimental Example 2 Example 2 0.1 93 0.10 Experimental Example 3 Example 3 0.1 95 0.15 Experimental Example 4 Example 4 0.1 90 0.10 Experimental Example 5 Example 5 0.1 92 0.10 Experimental Example 6 Example 6 0.1 95 0.05 Experimental Example 7 Example 7 0.1 96 0.15 Experimental Example 8 Example 8 0.1 95 0.15 Experimental Example 9 Example 9 0.1 95 0.10 Experimental Example 10 Example 10 0.1 95 0.12 Comparative Experiment Comparative example 0.07 92 1.00

1 and 2 are photographs of holograms recorded on the advertising molecule film produced according to Example 1, and photographs of object images recorded on the produced holographic film, respectively.

3 is a diagram showing diffraction efficiency during hologram recording according to Example 1. FIG.

Figure 4 is a photograph after one year of the hologram recorded on the advertising molecule film prepared according to Example 1.

Claims (12)

delete 1) 5 to 60% by weight photopolymerizable monomer; 2) 30 to 90 wt% binder; And 3) 0.001 to 10 wt% of initiator As an advertising molecule composition comprising: The photopolymerizable monomer is an advertising molecule composition, characterized in that at least one compound selected from the group consisting of compounds represented by the following formula 1-4 to 1-6, 1-9, or 1-11:  [Formula 1-4]

[Formula 1-5]

[Formula 1-6]

[Formula 1-9]

[Formula 1-11]

The method of claim 2, wherein the binder is polysulfone, polymethyl methacrylate, polystyrene methacrylate, and the advertising molecule composition, characterized in that at least one polymer selected from the group consisting of aromatic polyester. The advertising molecule composition of claim 2, wherein the initiator is a cationic photoinitiator or a radical photoinitiator. The method of claim 2, wherein the initiator is Cyracure UVI-6990, Cyracure UVI-6974, Degacure, SP-55, SP-150, SP-170, Irgacure 261, Irgacure 184, Irgacure 819, Irgacure 907, Irgacure 2959, Darocure 1173 , Darocure 4265, and Darocure 1664 is at least one compound selected from the group consisting of advertising molecule composition. Coating the advertising molecule composition according to claim 2 on a substrate and dried at 20 ~ 300 ℃ to form an advertising molecule film on the surface of the substrate. The method of claim 6, wherein the substrate is selected from the group consisting of silicon wafers, glass substrates, plastic films, and quartz. Advertising molecule film for hologram storage produced using the advertising molecule composition of claim 2. Advertising molecule molded product produced using the advertising molecule composition of claim 2. Ad molecule film prepared using the ad molecule composition of claim 2 having a shrinkage lower than 0.5% after hologram recording. The photopolymer film of claim 10, wherein the photopolymer film has a high diffraction efficiency of 90% or more. An optical recording medium comprising the advertising molecule film of claim 10.

Images