KR101037858B1 - Photochromic composition and product produced by the same - Google Patents

Abstract

The present invention relates to an outdoor photochromic composition comprising a photochromic dye and a metal ion and an outdoor article manufactured using the same. The outdoor photochromic composition may not only be photochromic but also thermally discolored, thereby reducing the discoloration rate by forming a complex compound, thereby exhibiting a large discoloration width even at a high temperature.

Photochromic, metal ions

Description

Photochromic compositions and articles made therefrom {PHOTOCHROMIC COMPOSITION AND PRODUCT PRODUCED BY THE SAME}

The present invention relates to photochromic compositions and outdoor articles made therefrom. In particular, the present invention relates to photochromic compositions and outdoor articles made therefrom, wherein the discoloration effect is not reduced even at high temperatures.

In general, in order to reduce the transmittance of sunlight to the window glass of automobiles, photochromic dyes are incorporated into resins and applied to window films having a light shielding effect. In addition, in order to block direct sunlight on the glass of a building, glass etc. which apply the colored film or vacuum-deposit a metal component on the surface are used similarly to the case of automobile.

However, when used for outdoor applications such as automotive glass or building glass, long-term exposure to solar as well as solar. However, in the case of the photochromic dye, since the decolorization rate by heat increases, there is a problem that the discoloration effect is reduced when used for outdoor use as described above. Specifically, in the case of the photochromic material applied in the prior art, as the temperature increases, the discoloration speed is increased, and the discoloration width is greatly reduced. Here, the discoloration width refers to the difference between the transmittance at the time of UV irradiation at each temperature when the transmittance at 100% when the UV is not irradiated at room temperature. Practically, when applied to vehicle or building glass, the discoloration effect is greatly reduced because the glass temperature rises above 40 ° C in summer.

Accordingly, there is a demand for the development of a technique for displaying a photochromic composition or a photochromic product used for outdoor use even at a high temperature.

When the present inventors add metal ions to a composition including a photochromic dye, the photochromic dye and the metal ion are not only discolored by the photochromic dye when exposed to light including UV, but also exposed to high temperature. It was found that the discoloration efficiency does not decrease even when exposed to high temperature for a long time due to the thermal discoloration by the interaction of and the slowing of discoloration by complex formation.

Accordingly, an object of the present invention is to provide an outdoor photochromic composition having excellent discoloration efficiency even after prolonged exposure to high temperature and an outdoor article manufactured thereby.

In order to achieve the above object, the present invention provides an outdoor photochromic composition comprising a photochromic dye and a metal ion and a method for producing the same.

The present invention also provides an outdoor article manufactured using an outdoor photochromic composition including a photochromic dye and a metal ion, and a method of manufacturing the same.

The outdoor photochromic composition and article according to the present invention may include not only photochromic dyes but also metal ions in addition to photochromic dyes and thermal discoloration, thereby reducing the discoloration rate by forming complex compounds, thereby exhibiting a large discoloration width even at high temperatures. .

Hereinafter, the present invention will be described in more detail.

In the present invention, the term 'outdoor use' means a use that is used by being exposed to high temperature by solar heat as well as light including UV. The present invention aims to provide a photochromic composition and article which does not reduce the discoloration effect upon exposure to high temperatures, so that it is excluded from the scope of the present invention to be used for outdoor use without being exposed to both light and high temperatures. In particular, the invention is more effective in applications that can be exposed to high temperatures of 40 degrees or more. Examples of the outdoor use include, but are not limited to, automobile glass, outdoor building materials, and the like.

Outdoor photochromic composition according to the invention is characterized in that it further comprises a metal ion in addition to the photochromic dye. In the present invention, by using a photochromic dye and a metal ion at the same time, not only the photochromic dye can induce discoloration by light, including UV, but also form a complex of the photochromic dye and a metal ion and the complex compound Can discolor by heat. That is, the outdoor photochromic composition according to the present invention may have an improved discoloration width at a high temperature by simultaneously expressing photochromic and thermochromic colors with only photochromic dyes even without using other types of dyes. In addition, in general, when the color change rate of the photochromic dye increases, the color change width is reduced, in the present invention, by using a metal ion photochromic dye and the metal ion to form a complex compound can reduce the color change rate, As a result, it is possible to prevent a decrease in color fading width.

In the present invention, as the photochromic dye may be used those known in the art, it is not particularly limited to the kind. For example, spirooxazine, benzopyran, napthopyran, chromeme, azo compound and the like. In the present invention, it is preferable to use a spirooxazine-based compound as a photochromic dye. Spirooxazine-based compounds have one more N / O than other dyes in the basic structure, which can be combined with metal ions, and especially when discolored, the N / O is present in the same plane. The above combination can be easily performed.

In addition, in the present invention, a new absorption occurs in the visible region by forming a complex of the photochromic dye and the metal ion, thereby reducing the visible light transmittance of sunlight. By using the above phenomenon, in the present invention, the difference in solar light transmittance is reduced by 5% or more at 25 ° C and 20% or more at 40 ° C or higher based on the ISO5090 standard representing solar light transmittance as compared with the case of using only photochromic dye. Can be.

In the present invention, the metal ions may take advantage of a transition metal ion, and the like More specifically, ^{Cu 2 +, Zn 2 +,} Mn 2 +, Fe 2 +.

The photochromic dye and the metal ion are preferably in an equivalent ratio of metal ions: photochromic dye = 0.2: 1 to 5: 1. When additives such as Hindered anime light stabilizers or antioxidants form chelates with metal ions, the equivalent ratio of additives such as HALS or antioxidant should be included in the equivalent ratio of photochromic dye.

A binder resin may be further added to the outdoor photochromic composition. In the case of using a binder resin, for example, polyester, polybutyral, acrylate-based monomers or polymers may be used, but not limited to these types and those known in the art may be used.

In particular, in this invention, it is preferable to use the polyfunctional (meth) acrylate type monomer which has two or more functional groups as binder resin. The multifunctional (meth) acrylate-based monomer having two or more functional groups provides a free volume at which the structural change of the photochromic dye can occur and at the same time provides a structure with low oxygen permeability.

Examples of the polyfunctional (meth) acrylate monomer having two or more functional groups include bisphenol A acrylate monomers; Polyalkylene glycol type di (meth) acrylate, other polyfunctional acrylate monomer, etc. can be used, These can be used individually or in mixture of 2 or more types . In the present invention, The multifunctional (meth) acrylate-based monomer having two or more functional groups is at least 50% by weight, preferably at least 70% by weight, more preferably 80% by weight in the photochromic composition for forming the photochromic film of the present invention. More than% may be included.

As the bisphenol A acrylate monomer, di (meth) acrylate may be preferably used, and specifically, BP4PA may be used.

Examples of the polyalkylene glycol di (meth) acrylates include bisphenol A ethoxylate di (meth) acrylates containing 2 to 20 ethoxy groups and repeating units 2 to 20 propoxy groups. Bisphenol A propoxylate di (meth) acrylate, bisphenol A alkoxylate di (meth) acrylate containing 2 to 20 epoxy groups and propoxy groups, bisphenol A glycerol dimethacrylate, bisphenol A glycerol Rate (1 glycerol / phenol) dimethacrylate, or mixtures thereof can be used.

Other polyfunctional acrylate monomers include dipentaerythritol hexaacrylate (DPHA), dipentaerythritol hydroxy pentaacrylate, pentaerythritol tetraacrylate, pentaerythritol triacrylate, trimethylene propyl triacrylate ( TMPTA), propoxylated glycerol triacrylate, trimethylpropane ethoxy triacrylate or mixtures thereof.

More specifically, it is preferable to use BP4PA, EGDA (ethlyeneglycoldiacrylate), EGDMA (ethyleneglycoldimethacrylate), DPHA (dipentaerythritol hexa acrylate), TMPTA (trimethylene propyl triacrylate) as the multifunctional (meth) acrylate monomer having two or more functional groups. In particular, it is preferable to use a mixture of BP4PA, ethlyeneglycoldiacrylate (EGDA) and ethyleneglycoldimethacrylate (EGDMA).

In the present invention, a vinyl monomer including an aromatic ring may be additionally added to the polyfunctional (meth) acrylate monomer having two or more functional groups. For example, styrene, divinylbenzene, or the like may be used. Can be. The vinyl monomer including the aromatic ring may serve to dissolve the photochromic dye. In the present invention, when using the vinyl monomer containing the aromatic ring it is preferably included in 30% by weight or less of the photochromic composition of the present invention.

In the present invention, when divinylbenzene (ethylene) and ethyleneglycoldimethacrylate (EGDMA) having short chain lengths are used, an appropriate degree of crosslinking and structure in forming a film or a product can be achieved by controlling the amount of these components. have. As a result, the film may have a structure having low oxygen permeability, thereby further improving durability of the photochromic product.

In the photochromic composition according to the present invention, the long chain monomer having 15 or more CC bonds positioned between the double bonds of the functional groups is at least 50% by weight, preferably at least 70% by weight, more preferably at least 80% by weight of the total monomers. It is preferred to be included. Long-chain monomers include BP4PA, 9-EGDA, and the like. In addition, in the photochromic composition according to the present invention, it is preferable that the number of C-C bonds located between the double bonds of the functional groups is less than 15 short chain monomers of less than 50% by weight of the total monomers. Short-chain monomers include EGDMA, DVB, hexaacrylate, pentaacrylate, triacrylate, and the like.

The outdoor photochromic composition according to the present invention may include an additive in a range that does not impair the object of the present invention. For example, a polymerization initiator, a stabilizer, a ultraviolet absorber, an antioxidant, a chain transfer agent, an IR absorber, an antifoaming agent, an antistatic agent, a mold release agent, etc. can be added.

Specifically, 2,2'-azobisisobutyronitrile, 2,2 '-(2,4-dimethylisovaleronitrile), 2,2'-azobis (4-methoxy to polymerize the monomers Azo polymerization initiators such as -2,4-dimethylvaleronitrile) and 1,1'-azobis (cyclohexane-1-carbonitrile), lauroyl peroxide, methyl ethyl ketone peroxide, and diisopropyl peroxane Peroxide type polymerization initiators, such as a cdidicarbonate and a dicyclohexane peroxydicarbonate, can be used.

Antioxidants include radical scavengers such as phenols, hydroxylamines, and lactones. The ultraviolet absorbers include triazines and benzos. Triazole (benzotriazole) series, benzophenone series, etc. are mentioned. Stabilizers include hindered amine light stabilizers. As the release agent, polydimethylsiloxanes (PDMS), polysiloxane polyether copolymers, fluorine-based surface treating agents, and the like may be used.

The outdoor photochromic composition according to the present invention may be prepared by mixing the photochromic dye and the material capable of providing the metal ion with a binder resin, a solvent, or other additives, if necessary. However, when using the polyfunctional (meth) acrylate type monomer which has two or more functional groups mentioned above as binder resin, a separate solvent is not needed.

As a material capable of providing the metal ion, a salt containing a metal ion may be used. For example, a halide of the metal ion may be used. When using the metal salt, the anion is Cl ^-, and the like _{^{-, Br -, ClO 4 -}} , NTf.

The present invention provides an outdoor article manufactured using the outdoor photochromic composition described above. The outdoor article is not limited to any kind of article for long-term exposure to high temperature as well as light, including UV outdoors. For example, film for automobile glass, outdoor building material, etc. are mentioned.

The outdoor article may be manufactured by molding the photochromic composition described above and, if necessary, by drying and / or curing before or after molding. For example, a film for automobile glass or an outdoor building material may be prepared by forming a photochromic composition as described above and drying or curing. The film forming method is not particularly limited, and for example, a casting method can be used.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the following Examples are provided to illustrate the present invention, and the scope of the present invention is not limited by these Examples.

<Production of composition>

Example

As binder resin, 60 parts by weight of BP4PA (based on 100 parts by weight of the binder resin, the same as below), 20 parts by weight of 9-EGDA, 10 parts by weight of styrene, and 10 parts by weight of DVB (divinylbenzene), Palatinate purple (James) 0.2 parts by weight of Robinson), 0.2 parts by weight of thermal initiator and ZnCl ₂ (molar equivalents such as Palatinate purple) were added, followed by stirring for about 2 hours to completely dissolve.

Comparative example

The composition was obtained in the same manner as in the Example except that ZnCl ₂ was not used.

Film manufacturing

The composition was injected between glass molds separated by a spacer of 300 μm, and then cured at 95 ° C. for 6 hours. The film obtained through the above process was again cured at 120 ° C. for 2 hours to prepare a film.

<Measurement>

1. Transmittance Measurement

After passing the ultraviolet light emitted from the UV illuminator (INNO Cure 100, JEIL UV co.) Through a filter transmitting the 365 nm region, irradiated with ultraviolet light corresponding to the total light amount of 1.35 mW / cm ² for 5 minutes, The transmittance was immediately measured using a UV-Vis detector. The UV irradiation condition is an amount corresponding to 87% of the energy (1.55 mW / cm ² ) corresponding to 350 ~ 380nm of the ultraviolet rays emitted from sunlight (AM1.5) is almost similar to the amount of ultraviolet rays of sunlight.

Was the result of using the method for measuring the transmittance, the case of using only Palatinate purple (comparative example), the most keot absorption at 604nm in the visible light range, in the case of using a Zn ^{2 +} as (example), there are two at 604nm and 642nm Absorption zones appeared. New absorption region appearing at 642nm is a new absorption region due to complex with Palatinate purple and Zn ^{+ 2.}

The results of the case where only the photochromic dye was included (comparative example) and the photochromic dye and the metal ion together (example) are shown in Table 1 below.

Transmittance (%) Temperature (℃) Palatinate only
(Comparative Example) Palatinate purple + ZnCl ₂ (Example) Wavelength (nm) 604 642 604 642 UV not irradiated 25 100 100 100 100 45 100 100 55 34 UV irradiation 25 12 50 12 7 45 61 86 30 14

As shown in Table 1, it can be confirmed that the light transmittance is lower at high temperatures when the photochromic dye and the metal ion are included together than when only the photochromic dye is included.

In addition, the transmittance was obtained by the following results when the solar transmittance was calculated based on the ISO5090 standard when irradiated with ultraviolet rays.

Temperature (℃) Palatinate only Palatinate purple + ZnCl ₂ 25 22 16 45 60 38

According to Table 2, it can be seen that the transmittance of sunlight is reduced by about 6% at 25 ℃, about 22% at 45 ℃ by the addition of metal ions.

Claims (17)

It includes a photochromic dye and a metal ion, and includes a multifunctional (meth) acrylate monomer having two or more functional groups as a binder resin, the equivalent ratio of the metal ion and the photochromic dye is 0.2: 1 to 5: 1 The photochromic composition for outdoor use. The photochromic composition for outdoor use according to claim 1, wherein the outdoor use is used for exposure to light and a high temperature of 40 ° C. or more. The method of claim 1, wherein the photochromic dye is selected from the group consisting of spirooxazine, benzopyran, napthopyran, chromeme, and azo compound Photochromic composition for outdoor use. The photochromic composition for outdoor use according to claim 3, wherein the photochromic dye is spirooxazine. The photochromic composition for outdoor use according to claim 1, wherein the metal ion is a transition metal ion. The method according to claim 5, wherein the metal ion is ^{Cu 2 +, Zn 2 +,} Mn 2 + , and the outdoor photochromic composition is selected from the group consisting of Fe ^{2 +.} delete delete delete The outdoor photochromic composition according to claim 1, wherein the multifunctional (meth) acrylate monomer having two or more functional groups comprises a bisphenol A acrylate monomer and a polyalkylene glycol di (meth) acrylate. The method of claim 10, wherein the multifunctional (meth) acrylate-based monomer having two or more functional groups are dipentaerythritol hexaacrylate (DPHA), dipentaerythritol hydroxy pentaacrylate, pentaerythritol tetraacrylate, A multifunctional acrylate monomer selected from the group consisting of pentaerythritol triacrylate, trimethylene propyl triacrylate (TMPTA), propoxylated glycerol triacrylate, trimethylpropane ethoxy triacrylate and mixtures thereof The photochromic composition for outdoor use. The outdoor photochromic composition according to claim 10, further comprising 30% by weight or less of the vinyl monomer including an aromatic ring in the photochromic composition. The photochromic composition for outdoor use according to claim 1, further comprising at least one additive selected from the group consisting of a polymerization initiator, a stabilizer, an ultraviolet absorber, an antioxidant, a chain transfer agent, an IR absorber, an antifoaming agent, an antistatic agent, and a release agent. Claim 1 to 6 and the method for producing an outdoor photochromic composition according to any one of claims 10 to 13 comprising the step of adding a substance capable of providing a metal ion to the photochromic dye and then mixing. An outdoor article manufactured using the outdoor photochromic composition of any one of claims 1 to 6 and 10 to 13. The outdoor article of claim 15, wherein the outdoor article is a film for automotive glass or an outdoor building material. A method for manufacturing an outdoor article comprising the steps of molding the outdoor photochromic composition of any one of claims 1 to 6 and 10 to 13 and curing the outdoor photochromic composition.