KR100874928B1 - Photochromic Photopolymer Compositions and Uses thereof - Google Patents

Abstract

The present invention relates to a photochromic photopolymer composition, a method of forming a photopolymer film using the composition, and a photochromic product made using the composition. The photochromic photopolymer composition of the present invention contains 1) a photopolymerizable monomer, 2) a binder, 3) a photochromic compound, and 4) an initiator, wherein the photopolymerizable monomer has a structure of formula 1,3,5- At least one compound selected from the group consisting of triazine-based unsaturated compounds, the photochromic compound may be any compound whose color is changed by the known light, preferably having a structure of formula (2).

Description

Photochromic Photopolymer Compositions and Their Uses {PHOTOCHROMIC PHOTOPOLYMER COMPOSITION AND USE THEREOF}

The present invention provides a photochromic photopolymer composition containing 1) a photopolymerizable monomer, 2) a binder, 3) a photochromic compound, and 4) an initiator, a method for forming a photopolymer film using the composition, and fabricating using the composition. To a photochromic product.

The photopolymer is a photopolymerizable organic polymer material, which is easy to process and has high sensitivity to light. The photopolymer which reacts by the mechanism which produces a polymerization difference according to the intensity of light generally consists of an acryl-type monomer, an epoxy monomer, an initiator, and a polymer binder. Unlike conventional photo plates, photopolymers are self-developing and fixing without a wet process, are simple to manufacture, and have the same thickness. Since it has a characteristic of having a diffraction efficiency of more than 2500 times, it is applicable to holographic recording materials in the form of write once read many (WORM), and recently, research for application to three-dimensional bit memory has been started.

Although such photopolymers have high applicability as a holographic medium, there is a problem in that holographic recording is reproduced when the reference light is irradiated after holographic recording, and the recording portion is not clear. In addition, since the photopolymer is recorded by the method in which the polymerization is caused by the interference light, there is a problem that secondary recording or decoding is difficult after recording.

As a technique for overcoming the above problems, there are known pulgides or pulgimides for holographic recording media capable of holographic recording using the principle that the photochromic material is discolored by a laser (Photochromic compounds for hologram recording, US Patent No. 4186002), which is discolored by room light or sunlight after recording, and the recording disappears, and has a disadvantage of low diffraction efficiency in holographic recording.

In addition, there is a known example where a gelatin film containing bacteriododoxin is applied to holography (14-Fluoro-Bacteriorhodopsin Gelatin Films for Dynamic Holography, US Patent No. 5518858), which also has low diffraction efficiency when recording holography, There is a problem that the recording disappears due to discoloration by sunlight.

Therefore, there is an urgent need to develop a photopolymer composition capable of increasing diffraction efficiency during holography recording and capable of secondary sensing or decoding and a method of manufacturing the same.

Accordingly, the present inventors, while studying a thin film of a diarylethene-based photochromic photopolymer, a polymer composition containing a photochromic material and a photocurable monomer can be recorded by holography, but in addition to the decoding by diffraction, the second optical The present invention has been accomplished by discovering that the rewritable holographic recording is possible.

It is therefore an object of the present invention to provide a photochromic photopolymer composition containing 1) a photopolymerizable monomer, 2) a binder, 3) a photochromic compound, and 4) an initiator.

Still another object of the present invention is to provide a coating method comprising applying a photochromic photopolymer composition as described above to a substrate to form a photopolymer film on the surface of the substrate.

Still another object of the present invention is to provide a product to which the photochromic photopolymer composition is applied or a film or a molded article made of the composition.

It is still another object of the present invention to provide a secondary sensing or decoding technique characterized by performing three-dimensional optical recording on the photopolymer film.

The present invention relates to a photochromic photopolymer composition comprising 1) a photopolymerizable monomer, 2) a binder, 3) a photochromic compound, and 4) an initiator, a method for producing a photopolymer film using the same, and a photopolymer film prepared as described above. It is about.

First, the present invention relates to a photochromic photopolymer composition containing 1) a photopolymerizable monomer, 2) a binder, 3) a photochromic compound, and 4) an initiator.

The component 1) the photopolymerizable monomer may be at least one compound selected from the group consisting of 1,3,5-triazine-based unsaturated compounds represented by the following Formula 1.

[Formula 1]

In the above formula,

At least one of R ¹ , R ² , and R ³ is -SR ⁴ -Q, and R ⁴ is C (═O), (CH ₂ ) _n C (= 0), (CH ₂ ) _n C (= O) (CH ₂ ) _m , C _n H _2n , (CH ₂ CH ₂ O) _n , C (= O) O, (CH ₂ ) _n C (= O) O, (CH ₂ ) _n C (= O ) O (CH ₂ ) _m , (CH ₂ ) _n SO ₂ , (CH ₂ ) _n SO ₂ (CH ₂ ) _m , (CH ₂ ) _n SO ₂ (CH ₂ ) _m OC (= O), (CH ₂ ) _n OSO ₂ , (CH ₂ ) _n OSO ₂ (CH ₂ ) _m , (CH ₂ ) _n OSO ₂ (CH ₂ ) _m OC (= O), (CH ₂ ) _n O (CH ₂ ) _m , Ar ¹ Or Ar ² SC (═O), n and m each independently represent an integer of 1 to 12, Ar ¹ and Ar ² represent a substituted or unsubstituted aromatic ring compound, Q Represents an acryl group, a methacryl group or an allyl group having 2 to 10 carbon atoms;

및 R⁷R⁸N-로 이루어진 군 중에서 선택되며, 상기 R⁵, R⁷, R⁸은 서로 같거나 다른 C₁ 내지 C₂₂의 치환 또는 비치환 알킬, C₅ 내지 C₂₂의 치환 또는 비치환된 시클로 알킬, 또는 치환되거나 비치환된 방향족 고리 화합물이며; R⁶는 C₁ 내지 C₁₅의 알킬렌 또는

자체가 방향족환을 나타낸다.When one or two of R ¹ , R ² , R ³ is -SR ⁴ -Q, the other one or two substituents are each independently R ⁵ NH—,

And R ⁷ R ⁸ N-, wherein R ⁵ , R ⁷ , and R ⁸ are the same as or different from each other C ₁ To C ₂₂ substituted or unsubstituted alkyl, C ₅ to C ₂₂ substituted or unsubstituted cycloalkyl, or substituted or unsubstituted aromatic ring compound; R ⁶ is C ₁ To C ₁₅ alkylene or

Itself represents an aromatic ring.

Examples of the compound having the structure of Formula 1 as described above include the following compounds:

[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

[Formula 1-5]

The binder of component 2) serves to bind each component contained in the composition, and all transparent polymers or organic and inorganic hybrids, which are commonly used as binders, may be used. For example, polysulfone, polymethylmethacryl What is selected from the group consisting of a latex (PMMA), polystyrene, polystyrene methacrylate copolymer, polyurethane, polyvinyl alcohol, polybutyl alcohol, carboxymethyl cellulose, polyimide precursor, aromatic polyester and the like.

The photochromic compound of component 3) may be at least one selected from the group consisting of known photochromic compounds and diarylethene-based compounds having the structure of Formula 2 below:

[Formula 2]

In the above formula,

R ⁹ is a bond line (connecting line), an alkylene group having 1 to 3 carbon atoms, or an alkylene group having 1 to 3 carbon atoms substituted with fluorine; Ar ³ and Ar ⁴ are each independently selected from the group consisting of a compound having the structure of Formula 3 and a compound having the structure of Formula 4; Z is a methylene group, a methylene group substituted with fluorine, a carbonyl group, or a CN group, and when Z is a CN group, R ⁹ is absent and the two Z groups are not connected to each other:

[Formula 3]

[Formula 4]

(In Formula 3 and Formula 4,

R ¹⁰ and R ¹³ are each independently an alkyl group having 1 to 3 carbon atoms unsubstituted or substituted with a fluorine atom; R ¹¹ is the same as R ¹⁰ and R ¹³ , or a hydrogen atom or a fluorine atom; R ¹² and R ¹⁴ are the same as R ¹¹ or C (═O) CH ₃ , a substituted or unsubstituted benzene ring, C (═O) (CH ₂ ) _n Ar ⁵ , (CH = CH) _n C (= O) Ar ⁶ , (OH) C = CAr ⁷ Ar ⁸ (The Ar ⁵ , Ar ⁶ , Ar ⁷ And Ar ⁸ means substituted or unsubstituted aromatic ring compound), phenylisoxazole group, hydroxymethylisoxazole group, alkyleneoxy alkyl ester group, aldehyde group, carboxylic acid group, C (= O) O (CH ₂ ) _n OC (= O) -C (R ¹⁵ ) _i = C (R ¹⁶ ) _j (R ¹⁷ ) _k ,-[CH = CH] _l- [C (= O)] _m [CH ₂ ] _n- [CH = CH] _o -C (R ¹⁸ ) _p (R ¹⁹ ) _q or -C≡CR ²⁰ Is; R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ And R ²⁰ are each independently a hydrogen atom, a C _{1 -22} alkyl group or a phenyl group; I, j, k, l, n and o are each independently an integer between 0 and 10; m is 0 or 1; p, and q are each an integer between 0 and 3, and have a relationship of p + q = 3; X and Y are each independently oxygen, nitrogen, sulfur atom or SO _2. )

Examples of the diarylethene-based compound having the structure of Chemical Formula 2 include 1,2-bis (2-methylbenzo [b] thiophen-3-yl) hexafluorocyclopentene (BTF6, Chemical Formula 2-1), 1, [6 '-(methacrylooxyethyloxycarbonyl) -2'-methylbenzo [b] thiophen-3'-yl-2- (2' '-methylbenzo [b] thiophen-3' '-Yl) hexafluorocyclopentene (MMBTF, formula 2-2), cis-1,2-bis (2-methylbenzothiophen-3-yl) -1,2-dicyanoethene (BTCN, formula 2-3), cis-1,2-dicyano-1,2-bis (2,4,5-trimethyl-3-thienyl) ethene (MTCN, formula 2-4), and the following formulas 2-1 to 2 The compounds shown in -21 can be mentioned:

[Formula 2-1]

[Formula 2-2]

[Formula 2-3]

[Formula 2-4]

[Formula 2-5]

[Formula 2-6]

[Formula 2-7]

[Formula 2-8]

[Formula 2-9]

[Formula 2-10]

[Formula 2-11]

[Formula 2-12]

[Formula 2-13]

[Formula 2-14]

[Formula 2-15]

[Formula 2-16]

[Formula 2-17]

[Formula 2-18]

[Formula 2-19]

[Formula 2-20]

[Formula 2-21]

 The diaryl ethene-based compound represented by Chemical Formulas 2-1 to 2-21 has excellent photochromic properties.

The material which can be used as the initiator of component 4) may be any initiator commonly used for polymer synthesis, for example, Igacure 184, Igacure 819, Igacure as a Ciba Specialty product or a Pulka product. One or more selected from 907, Igacure 2959, Darocure 1173, Darocure 4265, Darocure 1664 and the like can be used.

The photochromic photopolymer composition of the present invention contains 20 to 99.99 parts by weight of the photopolymerizable monomer, 0.001 to 80 parts by weight of the binder, 0.001 to 80 parts by weight of the photochromic compound and 0.001 to 30 parts by weight of the initiator. It is good. When the content range of the photopolymerizable monomer is out of the range, there is a problem in that no film is formed, and when the content of the binder is out of the range, the components cannot be properly combined, and the content of the photochromic compound is out of the range. In this case, there is a problem in that the photochromic property does not appear or agglomeration between compounds does not produce a transparent optical polymer, and when the content of the initiator is outside the above range, a sufficient and proper polymerization initiation does not occur.

If desired, the photochromic photopolymer composition of the present invention contains a compound selected from the group consisting of vinyl groups and acrylic unsaturated monomers, containing components 1) to 4) as described above, in order to improve photopolymerization speed and efficiency. It may further contain in an amount of 1 to 500 parts by weight based on 100 parts by weight of the composition. The vinyl group and the acrylic unsaturated monomer may be those having the structure of Formulas 5-1 to 5-12:

[Formula 5-1]

[Formula 5-2]

[Formula 5-3]

[Formula 5-4]

[Formula 5-5]

[Formula 5-6]

CH ₂ = CH-C (= O) SCH ₂ CH ₂ SCH ₂ CH ₂ SC (= O) -CH = CH ₂

[Formula 5-7]

[Formula 5-8]

[Formula 5-9]

[Formula 5-10]

[Formula 5-11]

[Formula 5-12]

In addition, the photochromic photopolymer composition of the present invention may further include one or more selected from the group consisting of 6) a polymer resin in order to improve the processability or physical properties of the coating film to be produced. The amount of the additional polymer may be 1 to 500 parts by weight based on 100 parts by weight of the photochromic photopolymer composition containing components 1) to 4) or components 1) to 5). As said additional polymer, polyvinyl chloride resin consisting of polyolefin, polycarbonate, polymethylmethacrylate, polyester, polyvinyl alcohol, polyimide, polyimide precursor, polysulfone, polybutyral, polyolefin or mixtures thereof chloride resins, polyvinyl acetate resins, vinyl chloride-vinyl acetate copolymers, polystyrene resins, styrene copolymers, phenoxy resins ( phenoxy resins, polyester resins, aromatic polyester resins, polyurethane resins, polycarbonate resins, polyacrylate resins, polymethacryl Polymethacrylate resins, acrylic copolyme rs), maleic anhydride copolymers, polyvinyl alcohol resins, modified polyvinyl alcohol resins, hydroxyethyl cellulose resins, carboxymethyl cellulose resins one or more selected from the group consisting of carboxymethyl cellulose resins and starches.

In addition, the photochromic photopolymer composition of the present invention is an amount of 5 to 95 parts by weight based on 100 parts by weight of a composition containing an organic solvent of components 1) to 4), components 1) to 5) or components 1) to 6). 7) The organic solvent may be used by selecting one or more selected from the group consisting of chloroform, tetrachloromethane and tetrachloroethane, or additionally methanol, ethanol, isopropanol, n-butanol, Methylisocarbinol, acetone, 2-butanone, ethyl amyl ketone, diacetone alcohols, isopropanone, cyclohexanone, NN Dimethylformamide (N, N-dimethylformamide), N, N-dimethylacetoamide (N, N-dimethylacetoamide), diethyl ether, diisopropyl ether, tetrahydrofuran ), 1,4-dioxane, 3,4-dihydro-2H-pyran, 2-methoxy ethanol, 2-e 2-ethoxy ethanol, 2-butoxy ethanol, ethylene glycol dimethyl ether, methyl acetate, ethyl acetate, isobutyl acetate isobutyl acetate, amyl acetate, ethyl lactate, ethylene carbonate; Aromatic hydrocarbons such as benzene, toluene, xylene, hexane, peptane, iso-octane, cyclohexane, methylene chloride, 1,2-dichloroethane, dichloropropane, chlorobenzene , Dimethylsulfoxide, N-methyl-2-pyrrolidone and N-octyl-2-pyrrolidone selected from the group consisting of 1 or more types can be used.

In addition, the photochromic photopolymer composition of the present invention, if necessary, more than 0.001 to 50% by weight relative to the total weight of the composition including antioxidants, thickeners, UV protection, waxes, charging agents, etc. commonly used in the art as needed. It may include.

Since the photopolymer composition according to the present invention has a photochromic property, such as an organic semiconductor, an optical recording medium, a display device, a recording device, a lens, an anti-counterfeiting film and a coating, a color changeable fiber, a color changeable container or a medicine, etc. It can be applied for various purposes.

The photochromic photopolymer 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 disk, optical head, holography media, optical recording, electrode, optical switch, display device, and / Alternatively, the present invention can be effectively applied to a sensor or the like.

In another aspect of the invention, the present invention, as one of the application method of the photochromic photopolymer composition according to the present invention, an object to be coated with the photochromic photopolymer composition, for example, silicon wafer, glass Coating on a substrate such as a substrate, plastic film, quartz, fiber, paper, wood, and drying at a temperature of -20 ° C to 300 ° C, preferably room temperature to 130 ° C to form a photopolymer film on the surface of the substrate. It provides a coating method comprising a. The thickness of the photopolymer film formed by the coating method is preferably 0.01 μm or more in order to exhibit appropriate photochromic properties of the composition constituting the photopolymer film. The method of coating the photochromic photopolymer composition on the substrate may be used as long as it is a coating method commonly used in the art, but is preferably a conventional solution coating method such as spin coating, flow coating, and bar. It is recommended to use coating, screen or spray coating methods.

As an exemplary embodiment of a photopolymer film according to an embodiment of the present invention, the photopolymerizable monomer represented by Formula 1-1, which is one of the derivatives of Formula 1 according to the present invention, and a derivative of the compound represented by Formula 2 Photochromic photopolymer membranes can be prepared by dissolving 2 g of the compound of Formula 1-1, 0.02 g of the compound of Formula 2-15, 2 g of polysulfone, and 0.02 g of Igacure 784 in 6 g of CHCl ₃ . After stirring for about 30 minutes at room temperature it was applied to the glass using a bar coater and dried at 60 ℃ for 6 hours to prepare a photopolymer film having a thickness of 200㎛.

As another application method of the photochromic photopolymer composition according to the present invention, the present invention is filled with the photochromic photopolymer composition in a mold for preparing a molded article, and then, about 130 ° C. or less, preferably room temperature to 130 ° C. It provides a method comprising the step of drying at a temperature to produce a final molded article.

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 and a coating, a color changeable fiber, a color changeable container or a pharmaceutical product to which the photopolymer 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 an advantage that the photochromic photopolymer composition according to the present invention can be easily decoded due to the difference in absorbance due to photochromic change.

According to the present invention, the photochromic photopolymer composition composed of 1) photopolymerizable monomer, 2) binder, 3) photochromic compound, 4) initiator, and photopolymer film produced therefrom have high diffraction efficiency and are deciphered by diffraction. In addition, there is an effect of providing a photopolymer that can be deciphered repeatedly by external light.

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

[ Example ]

material

The compound of formula 1 used in the following examples was synthesized according to the description of Korean Patent Application No. 10-2005-0084814, Canadian Patent CA2478719 and US Patent Application US20040006188, and the compound of Formula 2 was Japanese Patent Application JP2003176285, US It synthesize | combined and used according to the method known from patent US6787621, US patent application US2003118924, etc. In addition, the reagents used in the following examples were purchased from Aldrich Inc. [USA], TCI [Japan], Merck [Germany] or synthesized by a known method unless otherwise specified. The solvent used in the reaction was purchased from Aldrich (USA) or Deoksan Chemical in Korea.

[ Example  One]

0.1 g of the compound having the structure of Formula 1-1, 0.05 g of the compound having the structure of Formula 2-15, 0.05 g of polyshine violet, polymethylmethacrylate (molecular weight 30000) 0.05 g, poly 0.5 g of sulfone (molecular weight 35000) and 0.01 g of Igacure 784 (manufactured by Ciba-Geigi) were dissolved in a mixed solvent in 0.2 g of chloroform and 0.5 g of tetrachloroethane, and then stirred at 20 ° C. for 1 hour to cause photochromic composition. Was prepared. The composition was then applied to a glass substrate while rotating at 200 rpm using a spin coater. Then, the glass coated with the composition was dried in an oven at 40 ° C. for three hours and further dried at 60 ° C. for two hours to form a photochromic photopolymer film on the surface of the glass substrate.

 As a result, a photopolymer film having a thickness of 50 µm was produced. When 491 nm light was irradiated to the prepared film, holographic recording resulted in holographic recording with a diffraction efficiency of 90% (FIG. 1A), and when the light was irradiated with UV on the recorded portion, the color change was shown as in FIG. 1B. The color contrast was seven. When irradiated with visible light again, it returned to the original yellow color, but the holographic recording portion remained and the diffraction efficiency was maintained at 90%. The holographic recording portion was repeatedly readable by UV and visible light.

In this case, when the holographic recording film was irradiated with ultraviolet rays and visible light repeatedly, no phase separation phenomenon occurred, and photochromic phenomenon and diffraction phenomenon occurred, and thus the number of repeated cycles was 12,000 or more.

[ Example  2 to 10 and Comparative example ]

A photochromic photopolymer film was prepared in the same manner as in Example 1 except that the components and the method of preparing the photopolymer film were shown in Table 1 below.

[ Experimental Example Property measurement]

Physical properties of the photochromic photopolymer film prepared in Examples 1 to 10 and Comparative Examples, such as diffraction efficiency and photochromic contrast ratio, were measured by the following method.

(1) diffraction efficiency (%)

The holographic properties of the photopolymerizable film were measured as follows. A diode laser (532 nm) was used as a recording source, and polarization was controlled by a polarizer and plane waves were used by 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)

(2) Photochromic contrast ratio

After the holographic recording, the half of the recording area was covered and irradiated with ultraviolet light, and then the absorbance ratio between the exposed and unexposed areas of the UV light was measured (absorbance was measured by UV spectrometer).

Physical properties obtained as described above are summarized in Table 1 below.

Example Monomer (g) / initiator (g) Photochromic compound (g) Binder (g) / solvent (g) Film manufacturing condition temperature ( ^oC ) / drying time (hour) Diffraction efficiency (%) Photochromic contrast One Formula 1-1 (0.1) / Igacure 784 (0.01) Formula 2-15 (0.05) Poly methyl methacrylate (0.05) + poly sulfone (0.5 g) / chloroform (0.2) + tetrachloroethane (0.5) 40/3 + 60/2 90 7 2 Formula 1-2 (2) + Formula 1-10 (1) / Igacure 9074 (0.02) Formula 2-15 (0.1) + Formula 2-22 (0.3) Polysulfone (3) / Chloroform (1) + TCE (2) 60/12 92 5.5 3 Formula 1-3 (2) + Formula 1-10 (1) / Igacure 784 (0.01) Formula 2-1 (0.5) Polystyrene methacrylate copolymer (1) / dichloromethane (1) + acetone (0.5) 30/12 + 60/2 85 5.1 4 Formula 1-4 (2) + Formula 1-10 (1) / Igacure 784 (0.01) Formula 2-1 (0.5) + polyshine red (0.2) Polystyrene Metaacrylate Copolymer (4) / Methyl Isocarbinol (1) + TCE (2) 60/5 + 80/1 75 6.3 5 Formula 1-5 (2) + Formula 1-10 (1) / Igacure 784 (0.01) Formula 2-3 (0.5) Polyurethane (1) PMMA (1) / DMF (1) + THF (1) 40/12 + 60/10 82 3.7 6 Formula 1-3 (2) + Formula 5-6 (0.5) + Formula 1-10 (1) / Igacure 784 (0.03) Formula 2-4 (1.5) Polyvinyl Alcohol (1) / 2-Butoxy Ethanol (3) 40/12 + 60 (10) 78 4.1 7 Formula 1-2 (2) + Formula 5-10 (1) / Igacure 784 (0.01) Formula 2-5 (2.5) Polybutylal (3) / diisopropyl ether (1) + 1,4-dioxane (2) 30/12 + 60/10 65 2.5 8 Formula 1-2 (2) + Formula 5-10 (1) / Igacure 784 (0.01) + Darocure 1664 (0.005) Formula 2-6 (0.5) Carboxymethyl Cellulose (3) / Chloroform (1) + TCE (2) 40/12 + 60/20 75 5 9 Formula 1-2 (2) + Formula 5-10 (1) / Igacure 784 (0.02) + Methylene Blue (0.005) Formula 2-7 (0.5) + Formula 2-9 (0.5) Polyimide precursor (3) / chloroform (3) + ethylene carbonate (5) 40/3 + 80/12 + 110/5 76 4.2 10 Formula 1-2 (2) + Formula 5-10 (1) / Igacure 784 (0.02) + Methylene Blue (0.005) Formula 2-8 (0.5) + Formula 2-9 (0.5) Aromatic Polyester (1) + Polysulfone (4) / Chloroform (1) + TCE (2) 40/12 + 60/10 85 5 Comparative example Formula 1-2 (2) + Formula 5-10 (1) / Igacure 784 (0.02) 0 Polysulfone (3) / Chloroform (1) + TCE (2) 60/12 78 0

Polyshine violet

 Polyshine red

1A is a holographic recording photograph made according to Example 1,

FIG. 1B is a photograph showing a portion where color is changed after covering half of the recording film of FIG. 1A and irradiating ultraviolet rays.

Claims (10)

1) 20 to 99.99 parts by weight of the photopolymerizable monomer; 2) 0.001 to 80 parts by weight of the binder; 3) 0.001 to 80 parts by weight of the photochromic compound; And 4) 0.001 to 30 parts by weight of initiator As a photochromic photopolymer composition containing, The photopolymerizable monomer is at least one compound selected from the group consisting of 1,3,5-triazine-based unsaturated compounds represented by Formula 1 below, The photochromic compound is one or more selected from the group consisting of diarylethene-based compounds having the structure of Formula 2, Photochromic Photopolymer Compositions: [Formula 1]

In the above formula, At least one of R ¹ , R ² , and R ³ is -SR ⁴ -Q, and R ⁴ is C (═O), (CH ₂ ) _n C (= 0), (CH ₂ ) _n C (= O) (CH ₂ ) _m , C _n H _2n , (CH ₂ CH ₂ O) _n , C (= O) O, (CH ₂ ) _n C (= O) O, (CH ₂ ) _n C (= O ) O (CH ₂ ) _m , (CH ₂ ) _n SO ₂ , (CH ₂ ) _n SO ₂ (CH ₂ ) _m , (CH ₂ ) _n SO ₂ (CH ₂ ) _m OC (= O), (CH ₂ ) _n OSO ₂ , (CH ₂ ) _n OSO ₂ (CH ₂ ) _m , (CH ₂ ) _n OSO ₂ (CH ₂ ) _m OC (= O), (CH ₂ ) _n O (CH ₂ ) _m , Ar ¹ Or Ar ² SC (═O), n and m each independently represent an integer of 1 to 12, Ar ¹ and Ar ² represent a substituted or unsubstituted aromatic ring compound, Q Represents an acryl group, a methacryl group or an allyl group having 2 to 10 carbon atoms; When one or two of the R ¹ , R ² , R ³ is -SR ⁴ -Q, the other one or two substituents are each independently R ⁵ NH-,

And R ⁷ R ⁸ N-, wherein R ⁵ , R ⁷ , and R ⁸ are the same as or different from C ₁ to C ₂₂ substituted or unsubstituted alkyl, C ₅ to C ₂₂ substituted or unsubstituted cycloalkyl, or substituted or unsubstituted aromatic ring compound; R ⁶ is C ₁ to C ₁₅ alkylene or

Itself represents an aromatic ring; [Formula 2]

In the above formula, R ⁹ is a bond line (connecting line), an alkylene group having 1 to 3 carbon atoms, or an alkylene group having 1 to 3 carbon atoms substituted with fluorine; Ar ³ and Ar ⁴ are each independently selected from the group consisting of a compound having the structure of Formula 3 and a compound having the structure of Formula 4; Z is a methylene group, a methylene group substituted with fluorine, a carbonyl group, or a CN group, and when Z is a CN group, R ⁹ is not present and two Z groups are not connected to each other: [Formula 3]

[Formula 4]

(In Formula 3 and Formula 4, R ¹⁰ and R ¹³ are each independently an alkyl group having 1 to 3 carbon atoms unsubstituted or substituted with a fluorine atom; R ¹¹ is the same as R ¹⁰ and R ¹³ , or a hydrogen atom or a fluorine atom; R ¹² and R ¹⁴ are the same as R ¹¹ or C (═O) CH ₃ , a substituted or unsubstituted benzene ring, C (═O) (CH ₂ ) _n Ar ⁵ , (CH = CH) _n C (= O) Ar ⁶ , (OH) C = CAr ⁷ Ar ⁸ (wherein Ar ⁵ , Ar ⁶ , Ar ⁷ and Ar ⁸ represent a substituted or unsubstituted aromatic ring compound), phenylisoxazole group, hydroxy Methylisoxazole group, alkyleneoxy alkyl ester group, aldehyde group, carboxylic acid group, C (= O) O (CH ₂ ) _n OC (= O) -C (R ¹⁵ ) _i = C (R ¹⁶ ) _j (R ¹⁷ ) _k ,-[CH = CH] _l- [C (= O)] _m [CH ₂ ] _n- [CH = CH] _o -C (R ¹⁸ ) _p (R ¹⁹ ) _q or -C≡CR ²⁰ Is; R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ and R ²⁰ are each independently a hydrogen atom, a C _1-22 alkyl group or a phenyl group; I, j, k, l, n and o are each independently an integer between 0 and 10; m is 0 or 1; p, and q are each an integer between 0 and 3, and have a relationship of p + q = 3; X and Y are each independently oxygen, nitrogen, sulfur atom or SO ₂ . The photochromic photopolymer composition according to claim 1, wherein the photopolymerizable monomer is at least one selected from the group consisting of compounds represented by the following Chemical Formulas 1-1 to 1-5: [Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

[Formula 1-5]

The photochromic photopolymer composition of claim 1, wherein the photochromic compound is at least one selected from the group consisting of compounds represented by Formulas 2-1 to 2-21: [Formula 2-1]

[Formula 2-2]

[Formula 2-3]

[Formula 2-4]

[Formula 2-5]

[Formula 2-6]

[Formula 2-7]

[Formula 2-8]

[Formula 2-9]

[Formula 2-10]

[Formula 2-11]

[Formula 2-12]

[Formula 2-13]

[Formula 2-14]

[Formula 2-15]

[Formula 2-16]

[Formula 2-17]

[Formula 2-18]

[Formula 2-19]

[Formula 2-20]

[Formula 2-21]

The photochromic photopolymer composition according to claim 1, further comprising at least one compound selected from the group consisting of compounds represented by Formulas 5-1 to 5-12: [Formula 5-1]

[Formula 5-2]

[Formula 5-3]

[Formula 5-4]

[Formula 5-5]

[Formula 5-6] CH ₂ = CH-C (= O) SCH ₂ CH ₂ SCH ₂ CH ₂ SC (= O) -CH = CH ₂ [Formula 5-7]

[Formula 5-8]

[Formula 5-9]

[Formula 5-10]

[Formula 5-11]

[Formula 5-12]

The polyvinyl chloride resin of claim 1, wherein the polyvinyl chloride resin is composed of polyolefin, polycarbonate, polymethylmethacrylate, polyester, polyvinyl alcohol, polyimide, polyimide precursor, polysulfone, polybutyral, polyolefin or mixtures thereof polyvinyl chloride resins, polyvinyl acetate resins, vinyl chloride-vinyl acetate copolymers, polystyrene resins, styrene copolymers, phenoxy resins (phenoxy resins), polyester resins, aromatic polyester resins, polyurethane resins, polycarbonate resins, polyacrylate resins, polymethacrylates Polymethacrylate resins, acrylic copolymers, male Maleic anhydride copolymers, polyvinyl alcohol resins, modified polyvinyl alcohol resins, hydroxyethyl cellulose resins, carboxymethyl cellulose resins And starches, wherein the photochromic photopolymer composition further comprises at least one polymer selected from the group consisting of starches. Coating a photochromic photopolymer composition according to any one of claims 1 to 5 on a substrate and drying at 20 ° C. to 300 ° C. to form a photochromic photopolymer film on the substrate surface. Coating method. The method of claim 6, wherein the substrate is selected from the group consisting of silicon wafers, glass substrates, plastic films, quartz, and fibers. A photopolymer membrane prepared from the photochromic photopolymer composition according to any one of claims 1 to 5. A photopolymer molded article prepared from the photochromic photopolymer composition according to any one of claims 1 to 5. A photochromic product selected from the group consisting of an optical recording medium, a color changeable fiber, a color changeable container, and a color changeable drug to which the photochromic photopolymer composition according to any one of claims 1 to 5 is applied.

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