JPH0544657B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field] The present invention relates to a composite material that extends the dimming life of a material having a dimming function, ie, photochromic properties.

Substances that change color or become colored when exposed to light such as sunlight are called photochromic substances, and materials containing such photochromic compounds can be used for sunglass lenses, corrective lenses, and even window glass. It's been a while since it was proposed. Application to curtains and the like has also been proposed for the same purpose.

[Conventional technology]

Many compounds with photochromic properties have been found among organic and inorganic compounds (GH
Brown, “Photochromism,” Wiley
Interscience, New York (1971)).

On the other hand, several improvement proposals have been made with the aim of extending the dimming life of the above-mentioned photochromic compounds. For example, JP-A No. 58-34437 discloses that a transparent thin film of inorganic oxides such as sio, sio ₂ , Al ₂ O ₃ and ZrO ₂ is deposited on the surface of a plastic substrate containing an organic photochromic substance. A method for extending the dimming life is shown.

In addition, various spirooxazine compounds are known as examples of improvement proposals aimed at improving the dimming life of photochromic compounds (Japanese Patent Publication No. ^45-288-92 , Japanese Patent Publication No. 49-48631). , JP-A-48-23787, JP-A-55-36284).

[Problem that the invention seeks to solve]

Inorganic compounds generally have a small molecular absorption coefficient and a low color density. In addition, photochromic materials in which silver halide is dispersed in inorganic glass are used in many fields because they have color development properties after light irradiation, color decolorization properties after light blocking, and long service life. There is. However, this product can only be used for inorganic glass, and its applications are limited. Furthermore, there is a problem that there is almost no room for selection in the color tone after coloring.

On the other hand, organic compounds have the characteristics of large molecular extinction coefficients and large spectral changes, and various compounds have been proposed. Among them, spiropyran derivatives are one of the most representative, and have been used either by being dispersed in various binder resins and made into a film themselves, or by being coated on any support. However, this had the fatal drawback that it no longer had coloring properties after repeated color development and decolorization. Even if a spirooxazine compound, which is a photochromic compound that has improved these drawbacks, is used, the dimming life is short, which poses a practical problem.

Photochromic substrates obtained by attempting to extend the dimming life by coating with an inorganic oxide transparent thin film have major drawbacks, such as the formation of haze in the coating when heated.

The present invention improves the above-mentioned drawbacks and extends the dimming life.
The purpose is to improve heat resistance.

[Means for solving problems]

That is, in the present invention, the surface of the substrate containing the spirooxazine-based photochromic compound has an oxygen permeability coefficient of 100×10 ^-12 cm ³ cm/
The present invention relates to a photochromic molded product characterized by being coated with a transparent film having a pressure of less than cm ² sec.cmHg.

Any spirooxazine photochromic compound of the present invention can be used as long as it can be dispersed in various substrates.

Examples of currently known spirooxazine photochromic substances include the following.

Spirooxazine derivatives represented by the following general formula: Substituents R ¹ , R ² , R ³ and R ⁴ in the above formula are hydrogen or a hydrocarbon group having 1 to 20 carbon atoms, or a hydrocarbon group having a halogen group, a carboxy group, an ester group, a cyano group, an ether group, etc. group, X ¹ ,
X ² , Y ¹ , Y ² , Y ³ and Y ⁴ are hydrogen, an aryl group, a cyano group or a carboxy group, and have 1 or more carbon atoms.
6 alkoxy group, an alkyl group or carboxyalkyl group having 1 to 20 carbon atoms, a nitro group, a halogen group, a hydroxy group, a sulsanic acid group, and its metal base, and they are the same or different substituents.

A specific example of a spirooxazine compound is 1,3,3-trimethylspiro[indolino-
2,3'-naphtho[2,1-b](1,4)-oxazine]: 1,3,3,5-tetramethylspiro[indolino-2,3'-naphtho[2,1-b]
(1,4)-oxazine]:5-methyl-1,3,
3-trimethylspiro[indolino-2,3'-naphtho[2,1-b](1,4)-oxazine]: 1
-(β-carboxyethyl)-3,3-dimethylspiro[indolino-2,3'-naphtho[2,1-
b] (1,4)-oxazine]: 1-(β-carboxyethyl)-3,3,5-trimethylspiro[indolino-2,3'-naphtho[2,1-b] (1,
4)-Oxazine]: 5-methoxy-1-(β-carboxyethyl)-3,3-dimethylspiro[indolino-2,3′-naphtho[2,1-b](1,
4)-Oxazine]: 5-chloro-1-(α-cyanopropyl)-3,3-dimethylspiro[indolino-2,3′-naphtho[2,1-b](1,4)-
Oxazine] Substrates containing such photochromic compounds include various transparent or translucent plastic materials, such as various acrylic resins, polycarbonates, polyesters, particularly polyethylene terephthalate, cellulose acetate, cellulose propionate, Cellulose butyrate, polyvinyl butyral, polyvinyl chloride, polystyrene, polyamide, polyurethane, diethylene glycol bisallyl carbonate polymer, acrylotrile-(halogenated) styrene copolymer, epoxy resin, (halogenated)
Di(meth)acrylate polymers of bisphenol A and copolymers thereof, urethane-modified di(meth)acrylate polymers of (halogenated) bisphenol A and copolymers thereof, polysiloxane resins, and the like are preferably used.

The plastic material may be colored or dyed.

Various methods can be considered for preparing the substrate containing the photochromic compound, and the best method should be adopted depending on the purpose. Specific methods include a method in which a photochromic compound is mixed with a powder or granular plastic base material and then melt-kneaded; a photochromic compound is dispersed and dissolved in the monomer of the plastic material;
A method of polymerization, a method of dispersing a photochromic compound in a suitable solvent and then impregnating it into a plastic substrate, a method of dispersing the photochromic compound in a solution containing a suitable polymer and/or monomer, and optionally a solvent. After that, the photochromic compound is coated on the surface of various substrates such as inorganic glass, plastic, etc., and dried and/or cured. After dispersing the photochromic compound in a suitable solvent, it is coated on the plastic substrate and heated. Examples include a method in which a photochromic compound is transferred into a plastic substrate.

The photochromic compound is usually 0.05 to 30% by weight based on the matrix containing it, preferably
Contains about 0.1 to 20% by weight.

The substrate containing the spirooxazine photochromic compound obtained in this way has a final shape, such as a plate, a lens, a curved plate, a fiber, a sphere, a hemisphere, a column, a tube, and a circle. It may have a shape such as a cone, and may also be made of other transparent, translucent or opaque chromatic or achromatic substrates, such as plastic, metal, glass, ceramic, wood, concrete, paper, and various painted metals. A base material layer containing an organic photochromic compound may be laminated on a material such as , cloth, or the like. Examples of laminating methods include adhesion, lamination, coating (dipping, spin coating, flow coating, etc.), and casting.

The present invention provides that the surface of the base material containing the spirooxazine-based photochromic compound thus obtained has an oxygen permeability coefficient of 100×10 ^-12 made of an organic polymer.
It is obtained by coating with a transparent material of less than cm ³ cm/cm ² cm Hg.

In the present invention, a transparent film made of an organic polymer and having an oxygen permeability coefficient of 100×10 ⁻¹² cm ³ ·cm/cm ² ·sec.cmHg or less is defined as transparent, preferably having a haze of 20% or less. In other words, if the haze is higher than this, the light beam will not effectively reach the photochromic compound due to scattering phenomenon when the light beam is irradiated, and it will also be difficult to detect the photochromic phenomenon changed by the light beam with the naked eye. is likely to occur.

Here, the oxygen permeability coefficient is a measure representing the permeability of oxygen gas, and is a value defined as follows. That is, it is the amount (cm ³ ) of oxygen that permeates per unit time (sec) when the oxygen partial pressure difference is multiplied by 1 cmHg per unit area (cm ² ) on the surface of a flat plate with a thickness of 1 cm.

Oxygen permeability coefficient is 100×10 ^-12 cm ³・cm/cm ²・sec.cm
Specific examples of transparent materials below Hg include polyvinyl col, partially saponified polyvinyl acetate, polyacrylonitrile, cellulose, polyvinylidene chloride, polyvinylidene chloride/vinyl chloride copolymer, polycaprolactam, polyethylene terephthalate, polychlorinated Examples include vinyl and polyoxymethylene. Furthermore, it is also possible to add various organic and/or inorganic compounds to the above-mentioned transparent material within a range that satisfies the conditions for the oxidation permeability coefficient and does not impair transparency.

The oxygen permeability coefficient of the coated organic polymer is 100
If it is larger than ×10 ^-12 cm ³ cm/cm ² cm 2 sec.cmHg, there will be little coating effect and no extension of the dimming life can be expected. In order to make the film as thin as possible, the oxygen permeability coefficient must be 50×10 ^-12 cm ³ cm/cm ^{2 cm 2} sec.
A transparent film with a temperature of cmHg or less is preferable.

The transparent material is used by being coated on the surface of a substrate containing a spirooxazine-based photochromic compound, and the coating thickness is not particularly limited, but in order to make the effect more noticeable, it should be 0.01 micron or more. , preferably at a thickness of 0.1 micron or more.

Further, the upper limit of the coating thickness is not particularly limited, but from the viewpoint of shape retention, etc., 1 mm or less is usually used. Further, as a coating method, methods commonly used in the industry such as film adhesion, lamination, coating (tape coat, spin coat, flow coat, etc.) can be used.

Furthermore, for the purpose of increasing practicality, it is also possible to form various coatings on the surface before and/or after coating the transparent material. For example, a method of coating with various polysiloxane compounds is useful for the purpose of improving surface hardness. Further, for the purpose of improving adhesion, the substrate containing the spirooxazine-based photochromic compound can be subjected to primer treatment, such as polyurethane coating, or chemical treatment with acid, alkali, or the like.

Application examples of articles with extended dimming life obtained by the method of the present invention include sunglass lenses, corrective lenses, ski goggles, windshields, window glasses, show cases, toys, displays,
It is useful for mirrors, glasses, recording materials, lighting equipment umbrellas, camera lens filters, flower vases, automobile windshields or side windows, curtains, clothing, etc.

Example 1 Comparative Example 2 (1) Preparation of photochromic substrate 6-nitro-8-methoxy-5'-chloro-
0.05 parts of 1' ^, 3' ^, 3'-trimethylpyro [2H-1-benzopyran-2 ^, 2'-indoline] was added to 100 parts of n-butyl alcohol containing 10% by weight of polyvinyl butyral resin, and the mixture was stirred and dissolved. A coating liquid was obtained. This mixed solution was applied onto a glass plate by a flow coating method, and dried at room temperature for one day and night to prepare a base material containing an organic photochromic compound.

Next, 10 parts of a coating material made by dissolving 50 parts of polyvinyl alcohol (degree of saponification 88.0%, weight 1000) in 450 parts of water was applied to both the front and back sides of this base material.
Dip coating was carried out at a pulling speed of cm/min. The coating film was air-dried overnight at room temperature to obtain a photochromic substrate. Note that the thickness of the coating film was 6 microns. Also, the oxygen permeability coefficient is 10×10 ^-13 cm ³・cm/cm ²・sec.cm
It was Hg.

(2) Performance evaluation (A) Heat resistance test The photochromic substrate obtained in (1) above was
It was heated in a hot air dryer at ℃ for 1 hour. Thereafter, it was cooled to room temperature and irradiated with a chemical lamp as an excitation light source. When comparing the coloring state of the sample without heat treatment, no noticeable difference was observed. Further, as a comparative example, a similar test was conducted on a sample to which no coating material had been applied, and the color density of the heated sample was significantly lower than that before heating.

(B) Light resistance test After 80 hours of light irradiation using a fade meter, a color development test was performed using a chemical lamp, and almost no decrease in color density was observed. Further, as a comparative example, when a similar test was conducted on a sample to which no coating material was applied, almost no color developed.

Example 2 Comparative Example 2 As the photochromic-containing substrate, an "AO-PHOTOLITE" lens manufactured by American Optical was used.

(1) Preparation of photochromic substrate (A) Preparation of silane hydrolyzate A hydrolyzate was prepared by dropwise mixing 5.4 g of a 0.01N hydrochloric acid aqueous solution to 23.6 g of γ-glycidoxypropyltrimethoxysilane.

(B) Preparation of coating solution 15wt% aqueous solution of polyvinyl alcohol
After weighing 500 g in a beaker, 53.3 g of water, 18.2 g of the silane hydrolyzate, and 215 g of methanol-dispersed colloidal silica (average particle size 13±1 mμ) were respectively added under stirring.
In this case, 210 g of 1.4 dioxane, 0.5 g of a fluorine surfactant, and 3 g of aluminum acetylacetonate were added to the dispersion and thoroughly stirred and mixed to prepare a coating solution.

(C) Coating and curing Using the coating solution described above, apply the immersion method (pulling speed 5 cm/
It was applied for 2 hours and cured in a hot air dryer at 130°C for 2 hours. The thickness of the coating film is 4 microns, and the oxygen permeability coefficient is 20×10 ^-12 cm ³ cm/
It was ^cm2・sec.cmHg.

(2) Performance evaluation (A) Light resistance test After 100 hours of light irradiation using a fade meter in the same manner as in Example 1, a color development test was performed using a chemical lamp, and almost no decrease in color density was observed. Nakatsuta. In addition, when the same light irradiation test was performed on the samples without the coating material, the color density was considerably reduced.

Comparative Example 3 (1) Preparation of photochromic substrate (A) Preparation of photochromic-containing substrate The substrate containing the photochromic compound prepared in Example 1 was used.

(B) Preparation of silane hydrolyzate Add 100 parts by weight of Isopar E (hydrocarbon solvent) to 100 parts by weight of dimethylpolysiloxane (number average molecular weight 26,000) having silanol groups at both ends, dissolve it, and add 100 parts by weight of Isopar E (hydrocarbon solvent). 1 part by weight of acetoxysilane and 0.5 part by weight of dibutyltin acetate were added and mixed, and the mixture was left at room temperature overnight. Then further methyl isobutyl ketone
648 parts by weight and 432 parts by weight of cyclohexanone were added to prepare a coating solution.

(C) Coating and curing Using the coating solution described above, the photochromic compound-containing substrate described in (A) above was dip-coated at a pulling rate of 10 cm/min, and then coated at 100°C.
Heat cured for 30 minutes. The thickness of this transparent film is approximately 0.1 micron, and the oxygen permeability coefficient is
It was 2000×10 ^-12 cm ³・cm/cm ²・sec.cmHg.

(2) Performance evaluation (A) Light resistance test After 80 hours of light irradiation using a fade meter, a color development test was performed using a Kelcal lamp, and almost no color developed.

〔Effect of the invention〕

The photochromic-containing substrate obtained by the present invention has the following effects.

(b) Stability against light-induced deterioration is significantly improved.

(b) Effective in preventing thermal deterioration.

Claims (1)

[Claims] 1. The surface of a substrate containing a spirooxazine-based photochromic compound is coated with a transparent film made of an organic polymer and having an oxygen permeability coefficient of 100×10 ^-12 cm ³ cm/cm ² sec.cmHg or less. Photochromic molded products.