KR100289951B1 - Spirobenzopyran group-containing polymers, preparation methods thereof, and photochromic switch thin films using the same - Google Patents

Abstract

The present invention provides a spiro benzopyran group-containing polymer prepared from a spiro benzopyran group-containing monomer having an unsaturated end group represented by the general formula (1) and an aliphatic and / or aromatic comonomer having an unsaturated functional group, a method for preparing the same, Gwangho using the same A modified thin film and a photochromic switch element. According to the present invention, a polymer having excellent mechanical properties and exhibiting fast photochromic switch characteristics at room temperature is provided, and a method of manufacturing a photochromic thin film of a switch element is provided, and these can be used in various areas of an article such as an optical switch using photochromic properties. It is also useful for use in photochromic filters, light stabilizers, anti-counterfeiting banknotes and cards, display elements, optical recording media, and optical integrated elements.

[Formula 1]

[Wherein, R ¹ represents a linear or branched alkyl or alkenyl group having 1 to 22 carbon atoms, or a phenyl or phenylalkyl group, wherein the alkyl, alkenyl and phenyl groups described above are halides such as hydroxy, fluoride, glycidone It may be substituted by functional groups, such as ci, amine, vinyl, epoxy, (meth) acryl, amino, or mercapto;

R ² and R ³ each represent a hydrogen atom, a halogen atom, a cyano group, a substituted amino group, a nitro group, a substituted or straight chain or branched alkyl or alkoxy group having 1 to 10 carbon atoms;

R ⁴ is a substituted or alkylene or alkyleneoxy group having 1 to 22 carbon atoms and may include one or more heteroatoms selected from oxygen, sulfur, nitrogen, etc. in the carbon chain, and the aforementioned alkylene moiety is alkyl having 1 to 6 carbon atoms. May have one or more substituents selected from halides such as alkenyl, hydroxy, fluoride, glycidoxy, amine, vinyl, epoxy, (meth) acrylic, amino or mercapto;

Z is a group having at least one degree of unsaturation, for example a vinyl group and a (meth) acryl group;

X is a divalent linking group -CO-, -S-, -SO _2- , -C≡C-, -O-, -C (R ⁶ ) _2- , -C (R ⁶ ) = C (R ⁶ ) -, -N = N- or -NR ⁶ -and the like, wherein R ⁶ in the formula is each independently selected from the substituents defined for R ¹ , R ² and R ³ as defined above].

Description

Spirobenzopyran group-containing polymers, preparation methods thereof, and photochromic switch thin films using the same

The present invention relates to a spiro benzopyran group-containing polymer having a fast photochromic speed, thermal stability, and excellent processability, a method for preparing the same, and a photochromic switch thin film using the same.

Photochromatism changes color when exposed to light rays that include ultraviolet light (e.g., ultraviolet light or ultraviolet light in sunlight or mercury light, etc.), and then stops the light, irradiates another wavelength of light, or It is a reversible phenomenon exhibited by a compound that returns to its original color.

A series of pyran derivatives (US Pat. No. 3,567,605, US 5,238,981), including certain benzopyrans and naphthopyrans, thus exhibiting photochromatility, a series of spiroadamantane groups bound to the 2-position of the benzopyran or naphthopyran ring Of photochromic spiropyran derivatives (European Patent Publication No. 246,114, European Patent Publication No. 250,193), Spirooxazine Compounds (Japanese Patent Publication No. 3-81278, Patent Publication 92-8620, EP 0432 841 A2, EP 0600 669 A1, EP 0600 688 A1, etc. are known.

In addition, various applications are known which utilize the photochromatility of the compounds disclosed in the aforementioned documents. For example, a photoreactive plastic lens coated or impregnated with photo-variable spiropyran of European Patent Publication No. 246,114 is described, and European Patent 0442 166 A1 describes an illumination system, a lighting device, and the like, and a security card (WO 90). / 06539), optical switch (K. Sasaki, T. Nagamura, Appl. Phys. Lett., 1997, 71, 4, 434), photochromic glass (H. Nakazumi, R. Nagashiro, S. Matsumoto, K. Isagawa , SPIE, vol 2288, sol-gel optics, III, 1994, 402), recording media (Optical Engineering, 1995, 34, 480).

Among them, compounds having a spirobenzopyran skeleton have an advantage of simple synthesis compared to a spirooxazine type compound. Known compounds include spirobenzopyran compounds in which nitro groups, sulfonic acid groups, hydroxy groups and the like are substituted (JP 03 20,626, JP 02,264,246, JP 04,116,545, JP 04,116,546, EP 0414 476 A1, EP 0483 542 A1, EP 0502 506 A1, Etc.).

However, thin films prepared using polymer resins containing units derived from existing spirobenzopyran compounds having a spirobenzopyran skeleton have a problem of decomposing at 100 ° C. or higher, and also after the photo-pigmentation, an association is formed, resulting in the photochromatism rate. (Polymer, 1987, Vol 28, 1959, H. Eckhardt, A. Bose, VA Krongauz). These problems lead to the disadvantages of poor storage stability and light stability after optical tautomerisation.

A method of manufacturing a photochromic lens using a spirobenzopyran or an oxazine type compound is described in US Patent (US Patent 4,637,698), but in this case, the spirooxazine, which is a single molecule, is dispersed or dissolved in a polymer matrix. The lack of chemical bonds between the oxazine compound and the polymer matrix can lead to phase separation problems between the matrix polymer and the photochromic monomolecules, and after the photochromoic, agglomeration occurs when the single molecules become merocyanine to crystallize the polymer matrix. There are disadvantages. In addition, there arises a problem that the storage stability and optical thixotropy deteriorate after a long time use.

In addition, spirobenzopyrans substituted with an alkylcarbonyl group, an alkyl sulfonyl group, a halogen group, and an amino group are known (JP 05,181,227), but these compounds have a problem of slow photochromicity or low thermal stability.

Accordingly, a method has been proposed in which spirobenzopyran binds to a polymer matrix through chemical bonding. Among them, N-substituted spiropyran polymers (Macromolecules, 1984, 17, 1876 and Macromolecules, 1984, 17, 1225, Macromolecules, 1981, 14, 1382) are known, but in this case, the polymer chains are partially partially after photochromatility. There is a problem that the thermal stability is poor due to the filling or 6-position nitro group. N-substituted spirooxazine polymers (Macromolecules, 1992, 25, 3129) are limited in speeding up photochromatism.

In order to solve these problems, the present inventors have studied extensively on spirobenzopyran group-containing polymers that are thermally stable, have no problems of phase separation or association formation, and exhibit fast photochromic properties. 1 and spiro-benzopyran-Bz -X-R ⁴ -Z in the 6-position of the skeleton, such group (wherein, X is a divalent connecting group, Bz represents a benzene ring substituted with R ^3, R ⁴ is a divalent Spiro benzopyran compound substituted with a linking group, Z represents an unsaturated end group) showed a fast photochromic rate and excellent thermal stability, and among these spirobenzopyran compounds a spiro benzopyran compound having an unsaturated end group Not only do the polymers prepared as a polymer exhibit fast photochromicity rate, excellent thermal stability and processability, but also It found that it can also easily manufacture a photochromic switch thin film having a fast photochromic speed and excellent thermal stability from a solution obtained by dissolving the sheet and thereby completing the present invention.

1 is a ¹ H-NMR spectrum measured after dissolving the spirobenzopyran compound prepared in Reference Example 1 in CDCl ₃ ,

2 is a view showing a TGA showing a weight loss with respect to the heat of the spirobenzopyran compound prepared in Reference Example 1,

3 is a ¹ H-NMR spectrum measured after dissolving the spirobenzopyran polymer prepared in Example 1 in CDCl ₃ ,

4 is an infrared absorption spectrum of the spirobenzopyran polymer prepared in Example 1,

5 is a view showing a TGA of a polymer prepared in Example 4,

FIG. 6 shows changes in the spectral absorption spectrum of the thin film prepared in Example 7 when irradiated with short wavelength of 340 nm (light irradiation time, from top to bottom, 1 second, 49 seconds, 1 minute 37 seconds, 3 minutes 4 seconds, 4 minutes 46 seconds, 6 minutes 23 seconds)

7 is a view showing an optical switch effect on the short wavelength of 340 nm of the thin film prepared in Example 7.

Accordingly, a first object of the present invention is to provide a polymer comprising a unit derived from a spirobenzopyran compound represented by the following formula (1).

It is a second object of the present invention to provide a process for preparing a spirobenzopyran group-containing polymer.

It is a third object of the present invention to provide a polymer composition comprising a spirobenzopyran group-containing polymer.

It is a fourth object of the present invention to provide a polymer thin film comprising a spirobenzopyran group-containing polymer.

It is a fifth object of the present invention to provide an article comprising a spirobenzopyran group-containing polymer.

EMBODIMENT OF THE INVENTION Below, this invention is demonstrated in detail.

The spiro benzopyran group-containing polymer according to the present invention means a polymer containing units derived from a spirobenzopyran derivative of the general formula (1) in the polymer chain or attached to the polymer chain by chemical bonding. The spiro benzopyran derivatives of the general formula (1) used in the present invention are characterized in that the -Z group, which is substituted at the 6-position of the spirobenzopyran skeleton with X-Bz-R ⁴ -Z and the terminal -Z group has at least one degree of unsaturation.

[Formula 1]

[Wherein, R ¹ represents a linear or branched alkyl or alkenyl group having 1 to 22 carbon atoms, or a phenyl or phenylalkyl group, wherein the alkyl, alkenyl and phenyl groups described above are halides such as hydroxy, fluoride, glycidone It may be substituted by functional groups, such as ci, amine, vinyl, epoxy, (meth) acryl, amino, or mercapto;

R ² and R ³ each represent a hydrogen atom, a halogen atom, a cyano group, a substituted amino group, a nitro group, a substituted or straight chain or branched alkyl or alkoxy group having 1 to 10 carbon atoms;

R ⁴ is a substituted or alkylene or alkyleneoxy group having 1 to 22 carbon atoms and may include one or more heteroatoms selected from oxygen, sulfur, nitrogen and the like in the carbon chain, and the aforementioned alkylene moiety is alkyl having 1 to 6 carbon atoms. May have one or more substituents selected from halides such as alkenyl, hydroxy, fluoride, glycidoxy, amine, vinyl, epoxy, (meth) acrylic, amino or mercapto;

Z is a group having at least one degree of unsaturation, for example a vinyl group and a (meth) acryl group;

X is a divalent linking group -CO-, -S-, -SO _2- , -C≡C-, -O-, -C (R ⁶ ) _2- , -C (R ⁶ ) = C (R ⁶ ) -, -N = N- or -NR ⁶ -and the like, wherein R ⁶ is each independently selected from the substituents defined for R ¹ , R ² and R ³ as defined above].

Spirobenzopyran derivatives of formula (1) and methods for their preparation are described in the specification of the Korean patent application dated May 20, 1998 by the present inventors, and are incorporated herein by reference. According to the aforementioned Korean patent application by the present inventors, the spirobenzopyran derivative of Formula 1 may be prepared from substituted salicylic acid aldehyde and substituted indolin, and as an example, 6- [4 "-( 6 '''-(methacryloxyhexyloxyphenylcarbonyl)-1', 3 ', 3'-trimethylspiro [2H-1-benzopyran-2,2'-indolin] is 6-((hydroxy Hexyloxyphenylcarbonyl) -1 ', 3', 3'-trimethylspiro [2H-1-benzopyran-2,2'-indolin] can be prepared by reacting methacrylic chloride at room temperature in the presence of a catalyst. The ¹ H-NMR (CDCl ₃ ) spectrum of the synthesized spirobenzopyran compound shows characteristic peaks of the methacryl unit as the characteristic peaks and unsaturated end groups of the spirobenzopyran ring, as shown in FIG. 1. In addition, as for the thermal stability of the spirobenzopyran compound, as shown in Figure 2, From the TGA showing the weight loss, the thermal stability is very excellent from the decomposition start temperature of 226 ° C or higher.

In the above formulas, examples of the substituted or unsubstituted linear or branched alkyl group include hydrocarbon groups such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t -Butyl group, n-pentyl group, isopentyl group, neopentyl group, 1,2-dimethylpropyl group, n-hexyl group, cyclohexyl group, 1,3-dimethylbutyl group, 1-isopropylpropyl group, 1 , 2-dimethylbutyl group, n-heptyl group, 1,4-dimethylpentyl group, 2-methyl-1-isopropylpropyl group, 1-ethyl-3-methylbutyl group, n-octyl group, 2-ethylhex Real groups, 3-methyl-1-isopropylbutyl groups, 2-methyl-1-isopropylbutyl groups, 1-t-butyl-2-methylpropyl groups and n-nonyl groups; Alkoxyalkyl groups such as methoxymethyl group, methoxyethyl group, ethoxyethyl group, propoxyethyl group, butoxyethyl group, methoxyethoxyethyl group, ethoxyethoxyethyl group, dimethoxymethyl group, diethoxymethyl group, dimethoxyethyl group and diethoxy An ethyl group; And halogenated alkyl groups such as chloromethyl group, 2,2,2-trichloroethyl group, trifluoromethyl group, 1,1,1,3,3,3-hexafluoro-2-propyl group and the like.

In the above formulas according to the present invention, examples of substituted or unsubstituted alkylene groups may refer to those corresponding to those given as examples for the substituted or unsubstituted linear or branched alkyl group.

The spiro benzopyran compound of the formula (1) according to the present invention is substituted with -X-Bz-R ⁴ at the 6-position of the spiro benzopyran skeleton, and shows a fast photochromic rate and excellent photostability, so that the compound of formula (1) Can be advantageously used in a wide range of applications that utilize photochromic properties, such as optical integrated devices, optical switches, solar cells, photochromic filters, anti-counterfeiting notes or cards, photochromic fibers, cosmetics or ornaments, and light stabilizers. , Optical discs, display elements, or optical recording media.

Accordingly, the polymers of the present invention comprising units derived from the spirobenzopyran derivatives of the general formula (1) can also be applied to various fields of application using photochromic properties, for example, optical integrated devices, optical switches, solar cells, and photochromic filters. , Anti-counterfeiting banknotes or cards, photochromic fibers, cosmetics or ornaments, optical stabilizers, optical discs, display elements, or optical recording media.

According to a second object of the present invention, the spirobenzopyran group-containing polymer is selected from the group consisting of a spirobenzopyran monomer of the formula (1), a compound of the formula (2) and a compound of the formula (3), in the presence or absence of a solvent: One or more unsaturated functional group-containing monomers may be prepared by polymerizing by thermosetting or photocuring in the presence of an initiator.

[Formula 1]

Wherein R ¹ , R ² , R ³ , R ⁴ , Z and X are as defined above.

In the method of the present invention, the compounds of Formulas 2 and 3 may use commercially available compounds.

Specifically, the spiro benzopyran group-containing polymer of the present invention dissolves the spiro benzopyran compound of the formula (1) as a monomer and at least one compound selected from the compounds of the formulas (2) and (3) as comonomers in an arbitrarily selected organic solvent. And polymerizing the resulting mixture by heating it slowly for 0.5 to 150 hours, preferably 2 to 100 hours at a temperature of 30 ° C. to 150 ° C., preferably 40 ° C. to 120 ° C., in the presence of a commonly used thermosetting agent. It can be produced by the method characterized by.

In the spirobenzopyran group-containing polymer, the proportion of units derived from the spirobenzopyran monomer is not particularly limited, but is generally 0.01 to 99.99% by weight, preferably 0.1 to 99% by weight, more preferably 1 to 90% by weight. % to be.

As one example, the photochromic spirobenzopyran group-containing copolymer is 5% of 6- [4 "-(6 '' '-(methacryloxyhexyloxyphenylcarbonyl) -1', 3 in molar ratio as monomer. As a ', 3'-trimethylspiro [2H-1-benzopyran-2,2'-indolin] and comonomer, 67% styrene in molar ratio and 28% butyl methacrylate in molar ratio were dissolved in THF, followed by thermosetting agent. It is prepared by adding and refluxing under nitrogen atmosphere.

The average molecular weight of the polymer thus prepared is approximately 12,000, and the degree of dispersion (M _w / M _n ) is 1.68, so that the photochromic polymer can be obtained by dissolving in a solution and easy processing. The ¹ H-NMR (CDCl ₃ ) spectrum of the spirobenzopyran group-containing polymer thus prepared shows the characteristic peak of the spirobenzopyran backbone as shown in FIG. 3. In addition, the infrared spectral absorption spectrum of the spirobenzopyran group-containing polymer prepared above shows the characteristic peak of the spirobenzopyran skeleton as shown in FIG. 4.

10 mole% of 6- [4 "-(6 '' '-(methacryloxyhexyloxyphenylcarbonyl) -1', 3 ', 3'-trimethylspiro [2H-1-benzopyran-2,2 TGA, which represents a weight loss with respect to the heat of the spirobenzopyran group-containing polymer prepared from '-indolin', shows that the decomposition start temperature is 242 DEG C or more, which is very excellent in thermal stability.

In addition, the TGA showing the weight loss with respect to the heat of the spiro benzopyran compound thus prepared, as can be seen in Figure 2, shows that the thermal stability is very excellent as the start temperature is 226 ℃ or more.

The spirobenzopyran group-containing polymer according to the present invention is toluene. It can be dissolved in conventional solvents or mixtures thereof such as xylene, chloroform, acetone, acetonitrile, lower alcohol, dimethylformamide (DMF), dimethyl sulfoxide (DMSO) and the like.

As mentioned above, a third object of the present invention is to provide a composition comprising a spirobenzopyran group-containing polymer having excellent thermal stability, for example, according to the present invention, the following composition is provided:

Chloroform, hexane, acetone, acetonitrile, lower alcohol, 1,2-dichloroethane, dimethylformamide (DMF), water, dimethyl sulfoxide (DMSO), sulfolane, xylene, 3-nitro-α, α, α A composition comprising one or more solvents or mixtures thereof selected from the group consisting of trifluoronitrotoluene and the like and conventional organic solvents and a spirobenzopyran group-containing polymer according to the invention;

A composition further comprising at least one compound selected from the group consisting of tetraalkoxy silane, trialkoxyglycilyl silane, hydrochloric acid, organic acid, in the above-mentioned composition;

One or more resins selected from the group consisting of polyolefins, polystyrenes, polyvinylbutyrals, polycarbonates, polyesters, poly (meth) acrylates, polyurethanes, in the presence or absence of the aforementioned solvents and the spirobenzo according to the invention A polymer composition comprising a pyranic group-containing polymer.

The polymer composition of the present invention described above is at least one selected from the group consisting of α-methylnaphthalene, methoxynaphthalene, chloronaphthalene, diphenylethane, ethylene glycol, sulfolane, quinoline, dichlorobenzene, dichlorotoluene, propylene carbonate and xylene It may further contain a high boiling point solvent.

Although the composition ratio of each component in the polymer composition according to the present invention may differ depending on the use of the polymer composition, when the composition is used for preparing the photochromic thin film as described below, the spirobenzopyran group-containing according to the present invention. Preference is given to using the polymer in a proportion of 0.01 to 99.99% by weight of the total weight of the composition and other components in a proportion of 99.99 to 0.01% by weight. When each component in the polymer composition of the present invention is out of the composition ratio, it is not preferable because the mechanical properties of the resulting thin film is not good.

In addition, when the spirobenzopyran compound of the present invention is used in cosmetics, fibers, clays, and other compositions for light stabilizers or other purposes, the ratio of weight% may be used from 0.01 to several FPM units.

The above-described polymer composition of the present invention may be added various additives, lubricants, thickeners and the like that are obvious to those skilled in the art in order to improve heat resistance, mechanical properties, processing properties and the like.

As mentioned above, a fourth object of the present invention is to provide a photosensitive thin film containing a spirobenzopyran group-containing polymer, wherein the photosensitive thin film thus prepared has excellent photosensitivity to ultraviolet rays, visible light and near infrared rays in the region of 200 to 800 nm. There is a.

Such a photosensitive thin film is coated on a support such as a plastic resin, glass plate, aluminum plate, mylar film, conductive glass, etc., with a composition composed of a spirobenzopyran group-containing polymer according to the invention and any solvent and / or other polymers. It can be prepared by drying according to a conventional method, the photosensitive thin film thus prepared shows excellent absorbance in the wavelength range of 200 to 500 nm, and good absorbance in the wavelength range of 300 to 800 nm with respect to sunlight or ultraviolet rays. Indicates.

In preparing the photosensitive thin film according to the present invention, specific examples of the above-described support include a conductive electrode support selected from the group consisting of aluminum foil, aluminum drum, aluminum plate, platinum, mylar film, copper plate, conductive glass and conductive plastic. Or insulating supports selected from the group consisting of polypropylene, propylene carbonate, polymethacrylate, polyurethane and other plastics and glass.

In preparing the photosensitive thin film according to the present invention, as a coating method of the polymer composition that can be used, roll coating or spin coating, bar coating, spray coating, dip coating, and the like can be mentioned.

In another method, the spirobenzopyran group-containing polymer according to the present invention or a composition comprising the same may be selected from the group consisting of any solvent selected from the group consisting of ethers, alcohols, aromatic hydrocarbons, monoterpene hydrocarbons, liquid paraffin or mixtures thereof; Photochromic thin film comprising a method of mixing with the other conventional polymers mentioned above such as polyvinyl butyral (PVB), polycarbonate (PC), milling, coating on the support and optionally drying Can be prepared.

The spiro benzopyran group-containing polymer according to the present invention exhibits an absorption peak in the range of 200 to 800 nm while being capable of solution processing, and has a thermal stability of 240 ° C. or higher, so that it is a display device or an optical switch device, an optical integrated device, a solar cell, a sensor. It is highly applicable to other recording elements and optical elements.

Thus, the invention also comprises at least one spirobenzopyran group-containing polymer according to the invention, display elements, photochromic filters, optical switches, photosensitive drums, recording elements, solar cells, lenses, cosmetics , Articles such as fibers or optical elements.

Features and other advantages of the present invention as described above will be more clearly described with reference to the following examples, but the scope of the present invention is not limited only to the following examples.

Reference Examples 1-2 Preparation of Substituted Spirobenzopyranones

Reference Example 1 6- [4 ''-(6 '' '-(Methaacryloxyhexyloxyphenylcarbonyl) -1', 3 ', 3'-trimethylspiro [2H-1-benzopyran-2,2' -Indolin]

2.0 g (4.02 mmole) of 6-((hydroxyhexyloxyphenylcarbonyl) -1 ', 3', 3'-trimethylspiro [2H-1-benzopyran-2,2'- prepared according to the prior art Indolin] is dissolved in 50 ml of THF, triethylamine is added, and 0.51 ml (5.23 mmole) of methacrylic chloride is slowly added while stirring The reaction mixture is reacted under stirring at room temperature for 3 hours, and the resulting solid is filtered. The resulting solid is dissolved in dichloromethane and washed with saturated aqueous NaHCO ₃ solution, the organic layer is dried over anhydrous MgSO ₄ and purified by silica gel column chromatography to give 2.23 g (yield). 98%) 6- [4 "-(6"'-(methacryloxyhexyloxyphenylcarbonyl)-1', 3 ', 3'-trimethylspiro [2H-1-benzopyran-2,2'- Indolin] is obtained in the solid form.

The ¹ H-NMR (CDCl ₃ ) spectrum of the spirobenzopyran compound thus prepared shows characteristic peaks of the spirobenzopyran ring and terminal methacrylic units, as can be seen in FIG. 1.

In addition, TGA showing the weight loss with respect to the heat of the spiro benzopyran compound thus prepared, as shown in Figure 2, shows that the thermal stability is very excellent as the start temperature of decomposition is 226 ℃ or more.

IR (KBr, cm ⁻¹ ); 1718 (-COO-), 953 (C _spiro -O);

¹ H-NMR (300 MHz, CDCl ₃ ) δ 7.79 (d, 2H, J = 8.7 Hz), 7.60 (s, 1H), 7.57 (d, 1H, J = 8.1 Hz), 7.19 (t, 1H, J = 7.6 Hz), 7.10 (d, 1H, J = 7.1 Hz), 6.96-6.83 (m, 4H), 6.76 (d, 1H, J = 8.1 Hz), 6.56 (d, 1H, J = 7.7 Hz), 6.11 (s, 1H), 5.76 (d, 1H, J = 10.3 Hz), 5.54 (s, 1H), 4.18 (t, 2H, J = 6.6 Hz), 4.05 (t, 2H, J = 6.3 Hz), 2.74 (s, 3H), 1.83 (m, 2H), 1.73 (m, 2H), 1.57-1.38 (m, 4H), 1.32 (s, 3H), 1.17 (s, 3H);

¹³ C-NMR δ 10.7, 20.4, 26.1, 26.2, 26.3, 28.9, 29.3, 29.4, 32.4, 65.0, 68.4, 105.7, 107.3, 114.3, 115.0, 118.8, 119.8, 120.6, 121.9, 125.7, 128.1, 129.5, 130.7 , 130.9, 132.6, 132.9, 136.9, 148.4, 158.4, 162.8, 194.7. MS (m / z); 565 (M ⁺ , 75), 550 (17), 368 (8), 159 (100), 121 (13);

High-resolution MS; C ₃₆ H ₃₉ NO ₅ ; Theoretical Value: 565.2828, Experimental Value: 565.2832.

Reference Example 2 6- [4 "-(6" '-(methacryloxyhexyloxyphenylsulfanyl) -1', 3 ', 3'-trimethylspiro [2H-1-benzopyran-2,2'- Indolin]

6- (instead of 6-((hydroxyhexyloxyphenylcarbonyl) -1 ', 3', 3'-trimethylspiro [2H-1-benzopyran-2,2'-indolin] used in Example 1 (Hydroxyhexyloxyphenylsulfanyl) -1 ′, 3 ′, 3′-trimethylspiro [2H-1-benzopyran-2,2′-indolin], in the same manner as in Example 1 above. The compound is obtained in yield 98%.

IR (KBr, cm ⁻¹ ); 1718 (-COO-), 962 (C _spiro -O);

¹ H-NMR (300 MHz, CDCl ₃ ): δ 7.27 (d, 2H, J = 8.8 Hz), 7.15 (t, 1H), 7.08-7.02 (m, 3H), 6.94-6.80 (m, 3H), 6.75 (d, 1H, J = 10.2 Hz), 6.63 (d, 1H, J = 9.1 Hz), 6.51 (d, 1H, J = 7.7 Hz), 6.08 (s, 1H), 5.68 (d, 1H, J = 10.2 Hz), 5.52 (s, 1H), 4.14 (t, 2H, J = 6.6 Hz), 3.91 (t, 2H, J = 6.4 Hz), 2.70 (s, 3H), 1.82-1.66 (m, 4H ), 1.53-1.39 (m, 4H), 1.31 (s, 3H), 1.14 (s, 3H);

¹³ C-NMR δ 18.3, 20.1, 25.7, 25.8, 28.6, 28.9, 29.1, 51.8, 64.6, 67.9, 104.5, 106.8, 115.3, 115.9, 119.2, 119.5, 120.0, 121.5, 125.3, 126.7, 126.9, 127.6, 129.0 , 129.4, 132.7, 133.0, 136.5, 136.6, 148.1, 153.9, 158.6, 167.5;

MS (m / z); 569 (M ⁺ , 100), 554 (7), 469 (5), 444 (9), 380 (10), 159 (56);

High-resolution MS; C ₃₅ H ₃₉ NO ₄ S; Theoretical Value: 569.2600, Experimental Value: 569.2591.

Example 1-4 Preparation of Spirobenzopyrane Group-Containing Polymer

Example 1

6- [4 "-(6"'-(methacryloxyhexyloxyphenylcarbonyl)-1', 3 ', 3'-trimethylspiro [2H-1-benzopyran-2,2'-indolin] ( 0.5 g), styrene (1.23 g) and butyl methacrylate (0.72 g) were dissolved in THF, followed by addition of a thermosetting agent (1 mol%, 2,2-azobis (isobutylonitrile) (24 mg), followed by nitrogen The mixture was heated to reflux for 48 hours in an atmosphere, using the mixed solvent of ether and hexane to precipitate the polymer prepared above, and dried under reduced pressure at 50 ° C. to obtain a polymer which was purified in a yield of 50%. The temperature is 69 ° C., the weight average molecular weight is 12,000, and the dispersity (M _w / M _n ) is 1.68. Moreover, it has high solubility in organic solvents and is excellent in workability and can be used as a photochromic polymer.

The ¹ H-NMR (CDCl ₃ ) spectrum of the obtained polymer shows the characteristic peaks of the spirobenzopyran ring and the terminal methacrylic units, as can be seen in FIG. 3.

In addition, the infrared spectroscopic absorption spectrum of the spirobenzopyran compound thus prepared shows a characteristic peak of the unit derived from the spirobenzopyran monomer, as can be seen in FIG. 4.

Example 2

The procedure of Example 1 was followed by 0.082 g of 6- [4 ''-(6 '' '-(methacryloxyhexyloxyphenylcarbonyl) -1', 3 ', 3'-trimethylspiro [2H-1- Benzopyran-2,2'-indolin] was repeated in the same manner except that the yield of the polymer obtained was 1.05 g (56%) and the glass transition temperature was 66 ° C.

Example 3

The procedure of Example 1 was repeated in the same manner except that the reaction time was 72 hours. The yield of the polymer obtained is 52%, and the glass transition temperature is 70 ° C.

Example 4

The procedure of Example 1 was followed by 3.13 g of 6- [4 ''-(6 '' '-(methacryloxyhexyloxyphenylcarbonyl) -1', 3 ', 3'-trimethylspiro [2H-1- Benzopyran-2,2'-indolin] and the reaction was repeated for 24 hours The yield of the polymer obtained was 40%, weight average molecular weight 6000 and dispersion degree 1.71 The glass transition temperature is 85 DEG C. The decomposition initiation temperature of the obtained copolymer is 242 DEG C or higher, as shown in Fig. 5, and it can be seen that the thermal stability is excellent.

Example 5

6- [4 "-(6" '-(methacryloxyhexyloxyphenylcarbonyl) -1', 3 ', 3'-trimethylspiro [2H-1-benzopyran-2,2 prepared in Example 1 0.203 g of '-indolin' is mixed with 0.129 g of butyl methacrylate, 0.13 g of styrene and 0.5245 g of tripropylene glycol, and 0.04 g of dimethoxyphenylacetophenone (DMPA) is added to the resulting mixture. After coating on a glass plate, ultraviolet rays are radiated for 5 minutes under a stream of nitrogen to produce a transparent and excellent adhesive polymer.

Example 6

The procedure of Example 5 was prepared using the 6- [4 "-(6" '-(methacryloxyhexyloxyphenylsulfanyl) -1', 3 ', 3'-trimethylspiro [2H-1 prepared in Example 2. -Benzopyran-2,2'-indolin] is repeated in the same manner to obtain a polymer.

Examples 7 to 18 Preparation of the photochromic switch thin film

Example 7

0.2 g of the spirobenzopyran group-containing copolymer prepared in Example 1 is added to 2 ml of xylene, and the resulting solution is stirred at room temperature for 1 hour. The resulting solution was applied onto a glass plate using a spin coater and dried in an oven at 50 ° C. under reduced pressure for 12 hours to obtain a transparent photochromic thin film. When the obtained thin film was irradiated with short wavelength of 340 nm, it turned blue and no formation of association was found, and no phase separation phenomenon was found even when repeatedly irradiated with light.

Figure 6 shows the change in absorption spectrum of the thin film when the short wavelength of 340 nm was irradiated to the obtained thin film.

FIG. 7 shows the results of measuring the absorbance change effect of the thin film when the optical switch is operated by irradiating short wavelength of 340 nm for 1 second and blocking light for 5 seconds at 610 nm wavelength. Light coloration and dark attenuation due to light (optical switch efficiency = 100 x changed absorbance at dark attenuation / changed absorbance at light attenuation) respectively exhibit an efficiency of 95 to 100%.

Examples 8-18

The polymer thin film was prepared by repeating the procedure of Example 7 by changing the copolymer and solvent used and the preparation conditions as described in Table 1 below.

In all examples, no phase separation and association formation was observed, and no packing phenomenon was observed in the polymer matrix when the composition was prepared, after thin film preparation, and during the optical switch experiment.

The optical switch efficiency shown when the optical switch experiment was conducted by irradiating a short wavelength of 340 nm to the prepared thin film for 1 second and blocking light for 5 seconds was also shown in Table 1.

Example Copolymer Used (g) menstruum (mL) Coating method, drying temperature / hour Optical switch effect (%) 9 Example 1 0.050 THF One Spin coating, 50 ℃ / 3 hours 97 10 Example 2 0.2 xylene 2 Spin coating, 50 ℃ / 12 hours 11 Example 3 0.5 Toluene + Xylene (1: 4) Spin coating, 50 ℃ / 12 hours 95 12 Example 3 0.1 THF One Spin coating, 50 ℃ / 12 hours 99 13 Example 3 0.5 xylene 2 Bar coating, 50 ℃ / 10 hours 99 14 Example 3 0.5 xylene 2 Spin coating, 50 ℃ / 12 hours, spin coating again 96 15 Example 3 0.5 xylene 2.5 Bar coating, 25 ℃ / 12 hours 97 16 Example 4 0.5 xylene 2 Spin coating, 50 ℃ / 12 hours 80 17 Example 4 0.5 Xylene + Toluene (4: 1) 2.5 Spin coating, 50 ℃ / 12 hours 81 18 Example 5 - - - Spin coating, 50 ℃ / 12 hours - 19 Example 6 - - - Spin coating, 50 ℃ / 12 hours -

Example 20 [Comparative Example]

0.05 g of a commercially available nitrospyrrobenzopyran compound is dissolved in 1 ml of chloroform, and then 0.95 g of polymethylmethacrylate is added to the mixture, followed by stirring at room temperature to prepare a viscous spirobenzopyran compound composition. Then, the same process as in Example 7 was carried out to obtain a photochromic thin film.

The optical switch efficiency measured by irradiating a short wavelength of 340 nm to the thin film prepared here was about 70%, and both the light coloring and dark attenuation rates were slow. In addition, when the thin film produced here was irradiated for 1 hour or more, the formation of association was observed in the thin film, and the optical switch effect was slow.

According to the present invention, there is provided a spiro benzopyran group-containing polymer having a high speed of photochromicity, high thermal decomposition and excellent thermal stability, and excellent processability. Thin films can be prepared.

Claims (11)

A spirobenzopyran group-containing polymer, characterized in that it comprises units derived from a spirobenzopyran compound of formula [Formula 1] [Wherein, R ¹ represents a linear or branched alkyl or alkenyl group having 1 to 22 carbon atoms or a phenyl or phenylalkyl group, wherein the alkyl, alkenyl, phenyl or phenylalkyl group described above is halide such as hydroxy or fluoride , Substituted or unsubstituted with a substituent selected from the group consisting of glycidoxy, amine, vinyl, epoxy, (meth) acrylic, amino or mercapto; R ² and R ³ each represent a hydrogen atom, a halogen atom, a cyano group, a substituted amino group, a nitro group, a substituted or unsubstituted linear or branched alkyl or alkoxy group having 1 to 10 carbon atoms; Wherein the alkyl or alkoxy group described above is unsubstituted or substituted with a substituent selected from the group consisting of halides such as hydroxy, fluoride, glycidoxy, amine, vinyl, epoxy, (meth) acrylic, amano or mercapto; R ⁴ is a substituted or unsubstituted substituted or unsubstituted carbon atom having 1 to 22 carbon atoms, or a substituted or unsubstituted carbon atoms having 1 to 22 carbon atoms containing one or more hetero atoms selected from oxygen, sulfur, nitrogen in the carbon chain, or And an unsubstituted alkylene or alkyleneoxy group, wherein the alkylene moiety of the alkylene group or alkyleneoxy group described above is alkyl, alkenyl, hydroxy, halide, glycidoxy, amine, vinyl, epoxy having 1 to 6 carbon atoms. Substituted or unsubstituted with a substituent selected from the group consisting of (meth) acrylic, amino or mercapto; Z represents a group having at least one degree of unsaturation; X is -CO-, -S-, -SO _2- , -C≡C-, -O-, -C (R ⁶ ) _2- , -C (R ⁶ ) = C (R ⁶ )-, -N Divalent linking group selected from = N- or -NR ^6- , wherein the aforementioned R ⁶ are each independently selected from the substituents defined for R ¹ , R ² and R ³ as defined above]. The spirobenzopyran group-containing polymer according to claim 1, wherein Z represents a vinyl group or a (meth) acryl group. In the presence or absence of a solvent, the spirobenzopyran monomer of formula (1) is thermoset in the presence of an initiator and at least one unsaturated functional group-containing monomer selected from the group consisting of a compound of formula (2) and a compound of formula (3) Or polymerization by photocuring. [Formula 1] [Formula 2] [Formula 3] [Wherein, R ¹ represents a linear or branched alkyl or alkenyl group having 1 to 22 carbon atoms, or a phenyl or phenylalkyl group, and the alkyl, alkenyl, phenyl or phenylalkyl group described above is halide such as hydroxy, fluoride, Substituted or unsubstituted with a substituent selected from the group consisting of glycidoxy, amine, vinyl, epoxy, (meth) acrylic, amino or mercapto; R ² and R ³ each independently represent a hydrogen atom, a halogen atom, a cyano group, a substituted amino group, a nitro group, a substituted or unsubstituted straight or branched chain alkyl or alkoxy group having 1 to 10 carbon atoms, wherein the alkyl or alkoxy described above The group is unsubstituted or substituted with a substituent selected from the group consisting of halides such as hydroxy, fluoride, glycidoxy, amine, vinyl, epoxy, (meth) acrylic, amino or mercapto; R ⁴ is a substituted or unsubstituted substituted or unsubstituted carbon atoms having 1 to 22 carbon atoms, or a substituted or unsubstituted carbon atoms having from 1 to 22 carbon atoms containing one or more hetero atoms selected from oxygen, sulfur, nitrogen in the carbon chain, or An unsubstituted alkylene or alkyryleneoxy group, wherein the alkylene moiety of the alkylene or alkyleneoxy group described above is alkyl, alkenyl, hydroxy, halide, glycidoxy, amine, vinyl, Substituted or unsubstituted with a substituent selected from the group consisting of epoxy, (meth) acrylic, amino or mercapto; Z represents a group having at least one degree of unsaturation, X is -CO-, -S-, -SO₂-, -C≡C-, -O-, -C (R⁶)₂-, -C (R⁶) = C (R⁶)-, -N = N- or -NR⁶R represents a divalent linking group selected from⁶Is defined above^One, R²And R³on Each independently selected from substituents defined for. The solvent according to claim 3, wherein the solvent is tetrahydrofuran, toluene, lower alcohol having 1 to 10 carbon atoms, acetonitrile, acetone, water, dimethyl sulfoxide (DMSO), dimethylformamide (DMF), α-methylnaphthalene, Methoxynaphthalene, chloronaphthalene, diphenylethane, ethylene glycol, quinoline, dichlorobenzene, dichlorotoluene, propylene carbonate, sulfolane, xylene or a mixture thereof. The process according to claim 3 or 4, wherein the reaction is carried out at a temperature of 30 ° C to 400 ° C for 0.5 to 10 hours. A composition characterized in that it consists of at least one spirobenzopyran group-containing polymer according to claim 1 and a solvent or other polymer or mixtures thereof. 7. Acetone, acetonitrile, a lower alcohol having 1 to 10 carbon atoms, 1,2-dichloroethane, dimethylformamide (DMF), dimethyl soxide, tetraalkoxysilane, trialkoxysilane, di Alkoxysilane, hydrochloric acid, organic acid, pyridine, 1-methyl-2-pyrrolidone (NMP), sulfolane, sulfuric acid, water or mixtures thereof. 8. A polymer according to claim 6 or 7, wherein the other polymer described above is selected from the group consisting of existing general purpose resins such as polyvinyl butyral, polyolefin, polystyrene, polycarbonate, polyester, poly (meth) acrylate, polyurethane and the like. A composition characterized in that it is at least one species. 8. A solvent according to claim 6 or 7, wherein the solvent described above is α-methylnaphthalene, methoxynaphthalene, chloronaphthalene, diphenylethane, ethylene glycol, quinoline, dichlorobenzene, dichlorotoluene, propylenecarbonate, sulfolane, xylene or mixtures thereof The composition characterized in that it further contains a high boiling point solvent selected from the group consisting of. A thin film obtained by coating a composition according to claim 6 comprising a spirobenzopyran group-containing polymer on a support. The conductive support according to claim 10, wherein the support is selected from the group consisting of aluminum foil, aluminum drum, aluminum plate, platinum, mylar film, copper plate, conductive glass and conductive plastic, or polypropylene, propylene carbonate, poly A thin film characterized by an insulating support selected from the group consisting of methacrylate, polyurethane and other plastics and glass.