JPS6327837A - Photochromic material - Google Patents

Abstract

PURPOSE:To obtain the titled material having an improved responsibility and capable of preventing deterioration due to a continuous radiation of light and lowering of coloring density at a high temp. by dissolving a photochromic substance in a matrix contg. 2-15wt% a plasticizer on the weight basis of the solid matter thereof. CONSTITUTION:The high polymer matrix contains 2-15wt% plasticizer on the basis of the total solid matter thereof in the photochromic material contg. the photochromic agent in the high polymer matrix. The titled material is mounted on for example, a nylon film 1, and the photochromic agent 2 is composed of 1,3,3-trimethylindolino-6'-nitrobenzopyrilspiropyrane. The polyethylene terephthalate film 3, which is the matrix of the photochromic agent, contains 5wt% said photochromic agent on the weight basis of said agent. And 5wt% plasticizer of dioctylsebacate is dissolved in said film 3. Thus, the titled material having the responsibility capable of withstanding to applications of an automobile, an air craft and a building material, etc., and having a good coloring density at the high temp. and a long shelf life against the continuous radiation of light, is obtd.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) This invention relates to a photochromic material containing a photochromic agent in a polymer matrix.

(Prior art) As a conventional photochromic material, for example, the one shown in Fig. 3 (
There are those shown in al and (bl.
), a spiropyran-based photochromic agent is dissolved in polyvinyl alcohol (hereinafter referred to as PVA), and a nylon film 1
A film 7 (thickness: 5 μm to 15 μm) is coated on top. FIG. 3(b) shows a polyester resin as a matrix and spironaphthoxazine as a photochromic agent, and a polyester film 10 in which spironaphthoxazine is dissolved in a polyethylene terephthalate film (hereinafter referred to as P) as in FIG. 3(a).
ET) 9 and sandwiched between glasses 4 via a polyvinyl butyral interlayer 8 as shown in the figure.
It is a laminate.

The structure of such photochromic films and photochromic laminates has been described in detail in Japanese Patent Application Laid-Open No. 60-205429.

(Problems to be Solved by the Invention) However, in such conventional photochromic materials, the free volume of the matrix material was small, making it difficult for the photochromic agent molecules to change. Similarly, the response of photochromic materials is also slow, making them impractical for use in photochromic glass, canopies, and sunroofs for automobiles, aircraft, and building materials.

(Means for Solving the Problems) In order to solve these conventional problems, the inventors focused on adding a plasticizer to a polymer matrix containing a photochromic agent, and conducted a study experiment on the addition of a plasticizer. In the process of carrying out this process, it was found that if the plasticizer is less than 2% by weight based on the total solid content, it is ineffective, and if it exceeds 15% by weight, it deteriorates due to continuous light irradiation and the color density at high temperatures decreases.

The photochromic material of the present invention is based on the above knowledge, and in the photochromic material containing a photochromic agent in a polymer matrix, the polymer matrix further contains a plasticizer at a concentration of 2 to 15% by weight based on the total solid content. It is characterized by responsiveness that can withstand applications such as automobiles, aircraft, and building materials, color density at high temperatures, and long lifespan against continuous irradiation.

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

FIG. 1 is a diagram showing a first embodiment of the present invention.

First, the structure will be explained. 1 is a nylon film for supporting a photochromic material.

2 is a photochromic agent, which is 1.3.3-trimethylindolino-6'-nitrobenzopyrylspirobilane (hereinafter referred to as SP), and 3 is PET (Unitika ■υE3200), which is a matrix of the photochromic agent. SP is dissolved in PET at 5% by weight. It also contains 5% by weight of dioctyl sebacate (hereinafter referred to as DO3), which is a plasticizer.

Of course, photochromic agents are not limited to SP, but include all spiropyran-based, spirooxazine-based, a'zobenzene-based, and other Glen H Brown (GLF!NN, H
, BROWN) “Photochromism (Photo.

chromism) It goes without saying that it includes photochromic substances listed in J.

Further, the matrix resin is not limited to PET-based resins, and may include, for example, acrylic polymers such as polymethyl methacrylate, styrene-based polymers such as polystyrene, polyester-based polymers such as polycarbonate,
Polyether polymers such as polyethylene oxide, polyamide polymers such as nylon 6, olefin polymers such as polyethylene, cellulose polymers such as ethyl cellulose, polyvinyl alcohol, polyvinyl butyral, polyvinyl acetate, polyvinyl chloride, polyvinyl alcohol, polyvinyl butyral, polyvinyl acetate, polyvinyl chloride, vinylidene chloride, polyglycidyl methacrylate, polyurecne, poly-N-vinylcarbazole,
Examples include diethylene glycol bisallyl carbonate, copolymers thereof, and mixtures thereof, and they may be crosslinked if necessary.

Responsiveness was measured in the same manner as above for the photochromic material shown in FIG. 1 and a photochromic material prepared in the same manner except that the plasticizer DO3 was not included for comparison, and the results are shown in Table 2.

It can be seen from Table 2 that the photochromic materials of Examples have significantly improved responsiveness. This is because the free volume of the matrix around the photochromic molecules was increased by adding DOS.

FIG. 4 shows the results of coloring performance at high temperatures when the amount of DOS added was further increased.

As can be seen from this figure, as the amount of plasticizer increases, the color density at high temperatures (for example, 60° C.) decreases, and when it exceeds 15% by weight, almost no color is formed.

Therefore, the plasticizer concentration is preferably 15% by weight or less, preferably 10% by weight or less. Next, the plasticizer concentration and continuous irradiation light (Xe lamp, Ushio Inc @ IJXL-7502
5,000LX) is shown in FIG.

This figure shows that the durability with continuous irradiation light deteriorates as the concentration increases, so it is better to keep it at 15% by weight or less, preferably 10% by weight or less.
It can be seen that the weight percentage is good. Further investigation of the plasticizer concentration and responsiveness results in the results shown in Figure 6.

As shown in FIG. 6, it is not practical unless the plasticizer concentration is 2% by weight or more, and preferably 3% by weight or more.

From the above, the plasticizer concentration is preferably 2% by weight or more and 15% by weight or less, preferably 3% by weight or more and 10% by weight or less.

Of course, plasticizers are not limited to DOS, but include phthalates such as dibutyl phthalate and dioctyl phthalate, adipates such as dioctyl adipate, phosphates such as tricresyl phosphate, polyesters, polyethers, etc. All plasticizers such as triethylene glycol diacetate and mixtures thereof can be used.

Next, FIG. 2 shows a second embodiment.

In this example, a spironaphthoxazine derivative having the following formula was used as the photochromic substance, PVA was used as the matrix, and the spirooxazine concentration was 5% by weight. As a plasticizer, 5% by weight of triethylene glycol diacetate was dissolved. Polyvinyl alcohol 6 containing triethylene glycol diacetate to which spironaphthoxazine derivative 5 thus obtained was added was coated on nylon film 1.

For comparison with the photochromic material described above, the response was measured in the same manner as above for a photochromic material prepared in the same manner except that it did not contain a plasticizer, and the results are shown in Table 3.

Similarly, the relationship between high temperature coloring performance and plasticizer concentration, the relationship between deterioration resistance life due to continuous light and plasticizer, and the relationship between plasticizer concentration and response speed are shown in Figures 7.8 and 9, respectively. From these figures, it can be seen that the concentration of the plasticizer is preferably 2 to 15% by weight, preferably 3 to 10% by weight.

Of course, the support film is not limited to nylon, and any organic plastic film can be used, and it may also be a sheet instead of a film. Moreover, it is not limited to organic glass, and may be coated on inorganic glass. Needless to say, both the support and the matrix may be colorless or colored.

Further, the present photochromic material can be applied to all of the above-mentioned laminates.

(Effects of the Invention) As explained above, according to the second invention, the photochromic substance is dissolved in a matrix containing 2 to 15% by weight of plasticizer based on the solid content, so that the responsiveness is improved. A practical photochromic material has been obtained which has been significantly improved, is colored even at high temperatures, and has improved resistance to deterioration due to continuous light.The structure allows the photochromic agent to be dissolved in the matrix, allowing various coatings such as printing and transfer. There is an effect that

[BRIEF DESCRIPTION OF THE DRAWINGS] Figures 1 and 2 are cross-sectional views of a film provided with a film of the photochromic material of the present invention on a nylon support, respectively, and Figure 3(a) is a cross-sectional view of a film provided with a film of the photochromic material of the present invention on a nylon support. 3(b) is a sectional view of a laminate with a conventional photochromic material film between glass supports; FIGS. A curve diagram showing the relationship between the amount of plasticizer added and the absorbance change at 600 mm for the photochromic material of the example, and FIGS. 5 and 8 show the amount of plasticizer added and continuous irradiation light for the photochromic material of the first and second examples. Figures 6 and 9 are curve diagrams showing the relationship of deterioration due to
FIG. 3 is a curve diagram showing the relationship between the amount of plasticizer added and the response speed regarding the photochromic material of the second example. 1...Nylon film 2...1.3.3-) Limethylindolino 6"-
Nitrobenzopyryl spirobilane 3... Polyethylene terephthalate film containing dioctyl sebacate 4... Glass 5... Spironaphthoxazine derivative 6... Polyvinyl alcohol film containing triethylene glycol diacetate 7...・Polyvinyl alcohol film in which spiropyran is dissolved 8...Polyvinyl butyral interlayer film 9...Polyethylene terephthalate film
Written by Patent Attorney Ko Sugimura Figure 1 Figure 2 I Zelivinyl Alcohol Moon Mushroom Figure 4 Tsukasa'11 catties, 1; %'';r Desired speed a quantity, warehouse!% Figure 6 0 /Q 20
Figure 7 Addition amount of Town Bo I+, 4i1% Figure 8 shows τ

Claims (1)

[Claims] 1. A photochromic material containing a photochromic agent in a polymer matrix, characterized in that the polymer matrix further contains a plasticizer at a concentration of 2 to 15% by weight based on the total solid content.