JPH03115143A - Photochromic laminated glass - Google Patents

Abstract

PURPOSE:To obtain the laminated glass capable of increasing the selection range of the color tone ranging from the colored state to decolored state without deteriorating the coloring performance of a photochromic composition by interposing a colored sheet contg. dye and pigment and a sheet contg. the composition between >=2 glasses. CONSTITUTION:A photochromic composition layer 2, a transparent resin sheet 3 (polyvinyl butyral intermediate film) and a colored sheet 5 (colored polyvinyl butyral intermediate film) contg. dye and pigment are interposed between inorg. glasses 1 and 1 to form a laminated glass. The composition layer 2 is obtained by screen-printing a photochromic prepared according to the table on the surface of the transparent sheet 3, heating and drying the material. The sheets and film are laminated on one another in specified order, and the laminate is interposed between the glasses 1 and 1 and pressed at 140 deg.C and 12kg/cm<2> pressure for 30min to obtain the photochromic laminated glass consisting of the laminate shown in the figure.

Description

[Detailed description of the invention] (Industrial application field) The present invention relates to photochromic laminated glass.

(Prior Art) As a conventional photochromic laminated glass, there is one shown in FIG. 9, for example. In the illustrated laminated glass, 1 is glass, 2 is a photochromic composition layer, and 3 is a transparent sheet. The photochromic composition layer 2 is formed on the transparent sheet 3 by printing, dipping, spraying, or other operations. In addition, as shown in FIG. 10, a sheet 4 in which a photochromic composition is uniformly dispersed by kneading the photochromic composition into a resin is extruded and formed, and this sheet is sandwiched between glasses 1 to form a laminate. There is something like that.

(Problems to be Solved by the Invention) However, in such conventional photochromic laminated glasses, those shown in FIGS. 9 and 10 only contain a photochromic composition in a transparent sheet. As a result, the color tones and coloring densities of photochromic laminated glass in its colored and decolored states are limited, making it difficult to control the light of transportation such as cars and trains, window glass of buildings, or partitions. When used as glass, there is a problem that the range of selection is narrow and the applications for which it can be used are limited.

(Means for Solving the Problems) The present invention is intended to widen the selection range of color tones in the colored and decolored states of photochromic laminated glass, and includes a colored sheet containing dyes and pigments and a photochromic composition. The above-mentioned problems are solved by using sheets together and forming a laminated structure in which the sheets are sandwiched between at least two pieces of glass.

The photochromic laminated glass of the present invention consists of at least two sheets of glass and at least two or more transparent sheets sandwiched between these two sheets of glass, and among the transparent sheets, at least one transparent sheet The invention is characterized in that it contains a photochromic composition, and at least one other sheet has a dye or pigment dispersed therein.

In the present invention, a transparent sheet containing a photochromic composition is preferable to a colored sheet containing dyes and pigments.
It is preferable to provide it closer to the glass on the light irradiation side.

In a photochromic laminated glass according to a preferred embodiment of the present invention, at least one of the sheets excluding the transparent sheet containing the photochromic composition is a sheet in which a dye or pigment is dispersed.

In the present invention, the photochromic composition includes:
It is desirable to use a spironaphthoxazine derivative which has a large extinction coefficient in a colored state and has excellent durability against repeated coloring and decoloring. Of course, it is also possible to incorporate additives into the composition to improve durability.

(Example) The present invention will be described below with reference to the drawings.

A photochromic laminated glass shown in FIG. 1 was manufactured according to the following steps. In FIG. 1, 1 is inorganic glass, 2 is a photochromic composition layer, and these are formed on 3, a transparent resin sheet (polyvinyl butyral interlayer film). 5 is a colored sheet (colored polyvinyl butyral interlayer film) containing a dye or pigment. The choice of whether to use dyes or pigments is mainly a matter of convenience, and the color tone and amount of dyes or pigments to be added are a matter of preference, and these are important to the basic concept of the present invention. That's not the point.

First, the step of forming the photochromic composition layer in step 2 is to screen print a photochromic prepared with the formulation shown below on the surface of the transparent sheet in step 3 as shown in Figure 1, and then heat and dry it. Processed.

Ink formulation Next, stack these in a predetermined order and heat to 140°.
A laminate as shown in FIG. 1 was obtained by pressure bonding between glasses 1.1 under the conditions of a C1 pressure of 12 kg/cmz and a time of 30 minutes. What is important here is that the photochromic composition is not printed directly on a colored sheet, but rather on a transparent sheet, and the sheet containing the photochromic composition and the colored sheet are separated into two sheets and used together. It lies in being. The reason for this is that the dye contained in the colored sheet,
or more or less normal ultraviolet rays (300 to 38
0nm), therefore, if the photochromic composition is printed directly on a colored sheet, the coloring performance of the photochromic composition, which is sensitive to ultraviolet light (300 to 380n111) and colored, will be reduced. It's for a reason. However, in the case of a layered structure like the laminated glass of Example 1 shown in FIG. 1, the colored sheet and the sheet containing the photochromic composition are molded separately, so it is difficult to mix the dye, pigment, and photochromic composition. Since this can be avoided, the problem of deteriorating the coloring performance of the photochromic composition as described above can be solved. In fact, when measuring the change in absorbance with a spectrophotometer while irradiating the laminate shown in Figure 1 with a xenon lamp containing ultraviolet energy of 2.0 mW/cm, it shows exactly the same amount of change as when no colored sheet is used. was confirmed.

With the layer structure shown in Figure 1, the coloring performance of the photochromic composition is not degraded at all even when used in combination with a colored sheet, and the range of color tones in the colored and decolored states can be expanded. It turned out that it is possible.

This example differs from Example 1 in that instead of using a sheet printed with a photochromic composition, 1.0 parts by weight of the photochromic composition was uniformly kneaded into polyvinyl butyral resin and then extruded to form a photochromic composition. This is an example using a sheet 4 uniformly dispersed in the composition. In the same manner as in Example 1, these were stacked in a predetermined order and pressed together at a temperature of 140'C2 and a pressure of 12 kg/c for 30 minutes to obtain a laminate as shown in FIG. When the laminate shown in Figure 2 is irradiated with a xenon lamp containing ultraviolet energy of 2.0 mW/cm'' and the change in absorbance is measured with a spectrophotometer, it was confirmed that the change in absorbance was exactly the same as when no colored sheet was used. It was found that, as in Example 1, it is possible to widen the selection range of color tones in the colored state and the decolored state.

As shown in Fig. 3, this Example 3 differs from Examples 1 and 2 in that it contains dyes and pigments that have a partial concentration gradient, which is mainly used for front windows of passenger cars. This is an example in which a sheet 7 in which a photochromic composition is dispersed is used in combination with a colored sheet 6 in which a photochromic composition is dispersed partially, that is, with a concentration gradient, and the sheet is sandwiched between two pieces of glass and laminated. Generally, the partially colored sheet 6 is connected by an area B (blurred pattern) having a continuous density gradient in order to make the boundary line between the colored area A and the uncolored area C unclear. Therefore, when a sheet containing a photochromic composition is used in combination, it is easy to understand that when the photochromic composition is sensitive to ultraviolet rays and is colored, it is preferable that the coloring occurs with a concentration gradient in the BjI region. I can guess. If the dye or pigment used in the colored sheet and the photochromic composition are kneaded together and a co-extrusion method is used, it is possible to contain both at the same time with a concentration gradient, but as shown in Example 1. A problem arises in that the photochromic photosensitive coloring performance deteriorates due to the ultraviolet absorbing effect of dyes and pigments. It is extremely difficult in manufacturing to separate dyes, pigments, and photochromic compositions without mixing them, and process them into a single sheet with a similar concentration gradient. This example was made with attention to this problem, and after separately forming a colored sheet 6 having a concentration gradient and a sheet 7 containing a photochromic composition with a concentration gradient, The purpose is to solve a series of problems shown above by using a laminated structure.

First, a colored sheet in which dyes and pigments are dispersed with the concentration gradient shown in Fig. 3 is a method for producing a colored sheet with a shade band (polyvinyl butyral interlayer film), which is currently widely used in automobile front windows. Similarly, it can be obtained by using a co-extrusion method (T-die method) of molding through a slide die as shown in Japanese Patent Application Laid-Open No. 57-109615. The choice of whether to use dyes or pigments, as well as what color tone and concentration of dyes and pigments to use, is mainly a matter of convenience and preference, and this is not consistent with the basic concept of the present invention. It's not important. On the other hand, a sheet in which the photochromic composition is dispersed with the concentration gradient shown in FIG. 3 can be similarly obtained by coextrusion through a slit die. In this example, 1.0 parts by weight of a photochromic composition was kneaded with polyvinyl butyral resin and molded. The shape of the taper in region B of both sheets No. 6 and 7 can be freely shaped within the range that the shape of the slide die can be changed depending on the performance of the dye, pigment, or photochromic agent. These were laminated in a predetermined order and pressed together at a temperature of 140"C1 pressure of 1°2kg/C11" for 30 minutes to obtain a laminate as shown in FIG.

FIG. 4 shows the visible light transmittance of the laminate of Example 3 (FIG. 3) in a colored state and a decolored state. The visible light transmittance in the colored state is determined by applying ultraviolet light (3.0 mW/cm) to the above glass.
It was measured with a spectrophotometer while irradiating with a sequinon lamp containing energy of 00 to 380 nm). Looking at FIG. 4, it can be seen that the visible light transmittance changes continuously in the B ml region in both the colored state and the decolored state.

In this way, by forming the colored sheet and the photochromic-containing sheet with concentration gradients in region B to form a laminate as shown in FIG. 3, the colored state can be adjusted without deteriorating the coloring performance of the photochromic composition. , it is possible to widen the selection range of color tones in the decolored state, and furthermore, it is possible to create laminated glass whose visible light transmittance changes continuously (blurred pattern) in the B region in both the colored and decolored states. be.

This example is an example in which a different method was used for manufacturing the sheet containing the photochromic composition of Example 3. That is, instead of adding a concentration gradient to the photochromic composition, a concentration gradient is added to the ultraviolet absorber, and when the photochromic composition is sensitive to ultraviolet light and colored by using the ultraviolet screen effect of the ultraviolet absorber, B This is a method of continuously changing visible light transmittance in a region. Figure 5 shows its configuration.

A sheet containing an ultraviolet absorber having a concentration gradient in region B of 8 was molded using a coextrusion method through a slicing die as shown in Example 3.

Of course, the shape of the taper in region B can be freely formed as long as the shape of the slide die can be changed as needed. For the ultraviolet absorber, Tinubin 900 (manufactured by Ciba Geigy) was used, and 1.0 was added to the polyvinyl butyral resin.
Parts by weight were blended. Although Tinuvin 900 is used as the ultraviolet absorber here, the present invention is not limited thereto, and any ultraviolet absorber that exhibits the necessary ultraviolet screening effect can be selected depending on the performance of the photochromic composition. Next, a photochromic ink prepared with a photochromic composition as shown below was screen printed on the back side of the sheet No. 8 so as to cover area B as shown in FIG. 5, and then heated and dried for treatment.

Ink formulation These were stacked in a predetermined order and pressed together at a temperature of 140° C. and a pressure of 12 kg/cm” for 30 minutes to obtain a laminate as shown in FIG.

FIG. 6 shows the visible light transmittance of the laminate of Example 4 (FIG. 5) in a colored state and a decolored state. The visible light transmittance of the colored state is determined by applying ultraviolet rays (3.0 mW/cut) to the above glass.
It was measured with a spectrophotometer while irradiating with a xenon lamp containing energy (00 to 380 nm). Looking at FIG. 5, it can be seen that the visible light transmittance continuously changes in both the colored state and the decolored state in the B ml region, as in Example 3.

1111 This example is a method of continuously changing the visible light transmittance of the colored state of the photochromic composition in region B using the ultraviolet screen effect as in Example 4.
Instead of using a sheet containing a UV absorber fused into a tapered shape using a coextrusion process as shown in Example 4 (FIG. 5), dots of ink containing the UV absorber are provided. A case is shown in which gravure printing is performed on the surface of the transparent sheet 3 as shown in FIGS. 7 and 9 using a plate-making machine. In this Example 5, in order to print with a concentration gradient of the ultraviolet absorbent in the B area, an electronic engraving plate making machine was used and the engraving depth of the plate making area for the C area in FIG. 7 was set to 75 μm. The plate was made by engraving so that the engraving depth in the plate-making area for the plate-making area changed continuously from 75 μm to 5 μm from the C area to the H area. By engraving and making a plate in this way, it is possible to create a cell area in the B area that gradually becomes narrower from the C area toward the A eJf area.

Using the plate thus obtained, printing was carried out on the surface of a polyvinyl butyral resin sheet by gravure printing as shown in FIGS. 7 and 9 using the ink formulation shown below.

Ink formulation On the other hand, a photochromic composition layer was formed in the same manner as in Example 4 by screen printing on the back side of a polyvinyl butyral resin sheet as shown in FIG. 7 and 2. This sheet and the colored sheet 6 are overlapped in a predetermined order, and the temperature is 140.
℃, pressure 12 kg/elm".

Pressure bonding was carried out for 30 minutes to obtain a laminate as shown in FIG. FIG. 8 shows the visible light transmittance of the laminate of Example 5 (FIG. 7) in a colored state and a decolored state.

The visible light transmittance of the colored glass is 2.0 mW.
Measurement was carried out using a spectrophotometer needle while irradiating with a xenon lamp containing ultraviolet (300 to 380 nm) energy of 1.0 cm. It is observed that the visible light transmittance changes continuously in both the color state and the color state.

(Effects of the Invention) As explained above, according to the present invention, the structure is such that a sheet containing a photochromic composition and a colored sheet dispersing dyes and pigments are used together, and the sheet is sandwiched between two pieces of glass. Because of the laminated structure, it is possible to widen the selection range of color tones in a colored state and a decolored state without reducing the coloring performance of the photochromic composition.

In addition, when using a colored sheet that partially disperses dyes and pigments used for passenger car front windows together with a sheet containing a photochromic composition, it is possible to improve the coloring without reducing the coloring performance of the photochromic composition. In both the decolorized state and the B TiN region, it is possible to obtain a state in which the transmittance changes continuously (a blurred pattern).

Furthermore, in addition to the above effects, there are the following effects.

A situation in which a sheet containing a photochromic composition changes color due to deterioration of the photochromic agent may be observed, but when it is used in combination with a colored sheet as in the present invention, when a transparent sheet is used. Compared to this, discoloration due to deterioration can be made less noticeable. On the other hand, since the photochromic composition also acts as an ultraviolet absorber, the amount of ultraviolet rays irradiated onto the sheet containing dyes and pigments is reduced, thereby providing the effect of preventing photodeterioration of the dyes and pigments in the colored sheet.

[Brief explanation of drawings]

Fig. 1 is a cross-sectional view of a laminated structure of Example 1 using both a sheet containing a photochromic composition and a colored sheet, Fig. 2 is a cross-sectional view of a laminated structure of Example 2, and Fig. 3 is a cross-sectional view of a laminated structure of Example 3. FIG. 4 is a graph of visible light transmittance of Example 3, FIG. 5 is a cross-sectional view of the laminated structure of Example 4, and FIG. 6 is a graph of visible light transmittance of Example 4. , FIG. 7 is a cross-sectional view of the laminated structure of Example 5, FIG. 8 is a graph of visible light transmittance of Example 5, and FIG. 9 is a graph of the conventional structure in which the photochromic composition is partially printed on a transparent sheet. FIG. 10 is a cross-sectional view of a conventional laminated structure in which a photochromic composition is uniformly dispersed in a resin. 1...Glass 2...Photochromic composition layer 3...Transparent resin sheet (polyvinyl butyral interlayer film) 4...Sheet in which photochromic composition is uniformly dispersed 5...Dye and pigment are dispersed Colored sheet 6...Colored sheet 7 in which dyes and pigments are dispersed with a concentration gradient...Sheet 8 in which a photochromic composition is dispersed in a concentration gradient...Ultraviolet absorber with a concentration gradient Sheet 9 with dispersed... Ultraviolet absorber layer 1 Figure 3 Figure 4 Setting layer area Figure 5 Figure 6 Setting AN, area Figure 7 Figure 8 Setting tumor area

Claims (1)

[Claims] 1. Consisting of at least two sheets of glass and at least two or more transparent sheets sandwiched between the two sheets of glass, at least one of the transparent sheets is coated with a photochromic material. a composition containing at least one other
Photochromic laminated glass is characterized by using sheets in which dyes or pigments are dispersed. 2. The laminated glass according to claim 1, wherein the photochromic compound is a spirooxazine derivative.