JPH039344A - Photochromic molded body - Google Patents

Abstract

PURPOSE:To obtain a photochromic molded body having superior weather, chemical, heat and moisture resistances by using a polymer having a fluorine- contg. aliphatic cyclic structure as a matrix material. CONSTITUTION:An org. photochromic compd. is dispersed in a matrix made of a polymer having a fluorine-contg. aliphatic cyclic structure. The org. photo chromic compd. used is not especially limited if it is despersible in the polymer but a benzospirane compd., a spiroxazine compd., a dithizone mercury compd., or a phenazine compd. or a phenothiazine compd. is suitable for use as the org. photochromic compd. The shape of an org. photochromic molded body may be a plate, lens, column or cylinder shape. The molded body may be com bined with a quartz or glass base material as required. The weather, chemical, heat and moisture resistances are improved.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a photochromic molded article comprising an organic photochromic compound contained in a polymer having a fluorine-containing aliphatic ring structure.

[Prior Art] - Compared to inorganic photochromic compounds, organic photochromic compounds have a larger molecular extinction coefficient and larger spectral changes, and compounds having various absorption wavelengths have been proposed. In particular, spiropyran derivatives are one of the most typical photochromic compounds and have been used by being dispersed in various resins. However, there have been problems such as a short lifespan of developing and fading colors and insufficient practical properties such as weather resistance, chemical resistance, heat resistance, and moisture resistance.

[Problems to be Solved by the Invention] The present invention solves the drawbacks observed in photochromic molded products made of conventional materials as described above, and provides photochromic products with excellent weather resistance, chemical resistance, heat resistance, and moisture resistance. The purpose is to provide a new molded article.

[Means for Solving the Problems] Based on the recognition of the above-mentioned problems, the present inventor has made extensive studies and found that a polymer having a fluorine-containing aliphatic ring structure has high transparency, weather resistance, and chemical resistance. It has been newly discovered that it has heat resistance, moisture resistance, excellent moldability, and provides a matrix of sufficient strength, making it extremely advantageous as a substrate containing a photochromic compound.

Thus, the present invention has been completed based on the above findings, and provides a special hechromic molded article characterized in that an organic photochromic compound is dispersed in a matrix made of a polymer having a fluorine-containing aliphatic ring structure. This is a new offering.

The organic photochromic compounds that can be used in the present invention are not particularly limited as long as they can be dispersed in the base material, but preferred are benzospiropyran compounds, spirooxazine compounds, didizone mercury compounds, phenazine compounds, and phenothiazine compounds.

The shape of the IJ machine footchromic molded body in the present invention may be plate-like, lens-like, columnar, cylindrical, or the like. It is also possible to combine it with a base material such as quartz or glass if necessary.

In the present invention, the polymer having a fluorine-containing aliphatic ring structure may be exemplified over a wide range of examples, including those that are conventionally known or well-known. Therefore, in the present invention, a fluorine-containing polymer having the above-mentioned specific ring structure in the main chain is preferably employed.

For example, those having a ring structure as shown in the general formula % formula %) can be mentioned. Among these, polymers having the following ring structures are representative. However, the content of the present invention is not limited to these only.

There are two methods for producing these polymers. However, the method is not limited to these methods.

1. Cyclization polymerization (1) CF2CF2 ↓ Radical polymerization (USP 3202643, etc.) (3) CF2-CF-0-CF2-CF-CF3I Radical polymerization using a 2° cyclic upper pick (2) CF2" CF-CF2-CFCI-CF2-
CF-CF3I Radical Polymerization (USP 3978030) In the above, polymers having a perfluoroaliphatic ring structure were exemplified, but in the present invention, some of the fluorine atoms in substituted with a group,
Alternatively, those having a ring structure such as \CFCI/ obtained by metathesis polymerization may also be mentioned.

Therefore, the polymer having a specific ring structure in the present invention can be obtained more smoothly and advantageously by the above-mentioned cyclopolymerization, but in particular, the polymer having two polymerizable groups with different polymerizability in the molecule and By using a monomer in which the linear part of the connecting chain that connects these two polymerizable groups has 2 to 7 atoms, it is possible to reduce the side effects of gelation without using ultra-high pressure conditions or large dilution conditions. This allows the cyclization polymerization to proceed smoothly and advantageously while suppressing the occurrence of biochemical reactions.

As a monomer suitable for the above-mentioned cyclization polymerization, first of all, it is desirable that the monomer has two carbon-carbon multiple bonds having different polymerizability. Usually a carbon-carbon double bond is employed. For example, a fluorine-containing monomer with two non-symmetrical multiple bonds, a vinyl group and an allyl group, a vinyl ether group and a vinyl group, a fluorine-containing multiple bond and a hydrocarbon multiple bond, a perfluorinated multiple bond and a partially fluorinated multiple bond. Examples include: Secondly, it is desirable that the number of atoms in the straight portion of the connecting chain connecting these two carbon-carbon multiple bonds is 2 to 7. The number of atoms in the straight part of the connected chain is 0~
When the number is 1, cyclization polymerization is difficult to occur, and the same is true when the number is 8 or more. Generally preferred is a case where the number of atoms is 2 to 5.

Furthermore, the connecting chain is not limited to a straight line, and may have a side chain structure or a ring structure, and the constituent atoms are not limited to carbon atoms, but may include heteroatoms such as O, S, and N. . Thirdly, it is desirable that the fluorine content be 10% by weight or more. If the fluorine content is too low, the specificity of fluorine atoms will be difficult to exhibit. Naturally, perfluoromonomers are preferably employed.

Specific examples of the above-mentioned specific fluorine-containing monomer include CF2
"CFOCF2CF-Ch, CF2"CFOCF2C
hCF=CF2CF2"CFOCF2CFCF=CF2
．． CF2=CFOChOCF2CF=CF2CFz CF2”CFOCF2CF=C112,CF2”CFO
CF2CF2CH=CIh.

CF2=CFOCFtCF2C-CFz, CF2-
Ll: FD(CF2)20F=cFcFaCF3 Ch=CFCF2CF2CH=CTo, CF2''CF
CF2CFCH=CH2CFz CF2;CHOC)12CH2CF-C:F2. CH2
:CFCOCH2CH2CF=CF21 CH2=CH0CH2CH2CF2CF:CF2, etc. may be exemplified.

In the present invention, those having one vinyl ether group such as CF2''CFO- are preferably employed in terms of polymerization reactivity, cyclization polymerization, gelation suppression, etc. In particular, perfluoroallyl vinyl ether (CF2= CFOCF2CF
Suitable examples include CF2) and perfluorobutenyl vinyl ether (CF2=CFOCF2CF2CF=CF2).

The above-mentioned monomer components can be used alone or in combination of two or more, and there is no problem even if they are copolymerized in combination with other copolymer components to the extent that the essence of these components is not impaired. If necessary, the polymer may be crosslinked by some method.

Other monomers to be copolymerized are not particularly limited as long as they have radical polymerizability, and include fluorine-containing monomers,
A wide range of hydrocarbons and others may be exemplified. Of course, these other monomers may be used alone in radical copolymerization with the monomer capable of introducing the specific ring structure, or two or more of these other monomers may be used in combination to carry out the above copolymerization reaction. You can let them do it. In the present invention, it is usually desirable to select fluorine-containing monomers such as fluoroolefins and fluorovinylethers as other monomers. For example, preferred examples include tetrafluoroethylene, perfluoromethyl vinyl ether, perfluoropropyl vinyl ether, and perfluorovinyl ether containing a functional group such as a carboxylic acid group or sulfonic acid U. ,
It is also exemplified by chloro(.lifluoroethyl).

In order to take advantage of the characteristics of the specific fluorine-containing aliphatic ring structure aimed at in the present invention, it is preferable that the composition of the cyclic structure is 20% or more, and more preferably 4.
It is desirable that it is 0% or more.

In the present invention, as a method for crosslinking the fluorine-containing polymer, methods commonly known as (1) can be used as appropriate. Crosslinking can be carried out by feeding or by using radiation or the like.

Since the polymer having a specific ring structure in the present invention is soluble in fluorine-based solvents, it is also possible to create a thin protective film by casting from a solution. In addition, as a thermoplastic resin, it has a low melting temperature and a relatively low melt viscosity, so it is easy to heat melt.

The solvent used is not limited as long as it dissolves the above polymer, but perfluorobenzene, °°°
Afluid (Product name: Fluorinated solvent manufactured by Asahi Glass Co., Ltd.)
, Paflorinade' (Product name: Liquid containing perfluoro(2-butyltetrahydrofuran) manufactured by 3M)
, trichlorotrifluoroethane and the like are preferred. Naturally, two or more appropriate types can be used in combination as a solvent. Particularly in the case of mixed solvents, hydrocarbons, alcohols, and other organic solvents can also be used in combination. Solution concentration is 0.01wtχ~50wt! and preferably 0.1wt
It is $~20wt$.

Application examples of the photochromic molded article obtained by the present invention include recording materials, photochromic lenses, displays, etc.

[Examples] Next, Examples of the present invention will be described in more detail, but it goes without saying that this description does not limit the present invention.

Synthesis example] 35 g of perfluoroallyl vinyl ether, trichlorotrifluoroethane (hereinafter abbreviated as R113)
5 g of ion exchange water, 150 g of ion-exchanged water, and 35 mg of (C3F7C00)2 as a polymerization initiator in an internal volume of 200 m
The mixture was placed in a pressure-resistant glass autoclave. 3 within the system
After purging with nitrogen twice, suspension polymerization was carried out at 26°C for 23 hours. As a result, 28 g of polymer was obtained.

When we measured the infrared absorption spectrum of this polymer, we found that
1790cm- due to the double bond present in the monomer
+, there was no absorption near 1840 cm-+. In addition, this polymer was dissolved in perfluorobenzene and +9]I
When the NMR spectrum of I' was measured, a spectrum showing the following repeating structure was obtained.

1-'”FC-75 (trade name: liquid whose main component is ba-fluoro (2-butyltetrahydrofuran) manufactured by 3M Company, hereinafter abbreviated as FC-75), 0°5 at 30°C in medium
It was 30. The glass transition point of the polymer is 69°C, and it is a tough, transparent, glass-like polymer at room temperature. The 10% thermal decomposition temperature is 462°C, and the light transmittance is 9.
It was as high as 5%.

Synthesis Example 2 20 g of 1,1,2,4,4,5.5-heptafluoro-3-ogicar 1,6-hebutadiene and Rnie i13
40g of was placed in a Mitsuro flask heated with nitrogen, and 20+ng of (C3F7C00)2 was added as a polymerization initiator.
After further purging the system with nitrogen, polymerization was carried out at 18°C for 10 hours. As a result, 10 g of polymer was obtained. This polymer is R
It is a polymer that dissolves in -113 and has an intrinsic viscosity [? 7] is 0.9
It was 6. It was confirmed by 19F and IH NMR that it was a polymer having a ring structure in the main chain.

In addition, this polymer is colorless and transparent, and has a light transmittance of 93.
% was high.

Example 1 The fluorine-containing polymer obtained in Synthesis Example 1 was converted into FC-7.
It was dissolved in 5. (Solid content concentration 10Wt2:) 10 parts of R113 and 6-nito U are added to 100 parts of this polymer solution.
-8-Methoxy-1',3',3°-towamethyl subi I
A mixed solution consisting of 0.005 part of 7[2H-1-benzobiran-2,2-indoline] was added. The solution thus obtained was cast onto a quartz plate under a nitrogen stream.
A photochromic molded article was prepared by drying at 65° C. for a day and a night.

This photochromic molded body was heated at 30°C190~95X.
After being left in an RH atmosphere for 24 hours, it was heated in a hot air dryer at 80°C for 1 hour. When the color development state was measured by light irradiation after cooling to room temperature and compared with that which had not been humidified or heated, no difference was observed at all.

Example 2 The fluorine-containing polymer obtained in Synthesis Example 2 above was dissolved in meta-xylene hexafluoride. (Solid content concentration iow
tχ) Add 10 parts of chloroform to 100 parts of this polymer solution.
and 6-nitro-8-methoxy-1°3ZT-trimethylsubilane-17[2H-1-benzene-biran-2,
A mixture consisting of 0.005 part of 2'-indoline] was added. The solution thus obtained was cast onto a quartz plate and dried under a nitrogen stream at 65°C for a day and night to prepare a photochromic molded body.

When this molded product was subjected to a color development test in the same manner as in Example 1, no difference was observed between the molded product and the molded product that had not been subjected to humidification and heat treatment.

Example 3 A photochromic molded article was prepared in the same manner as in Example 1, except that the fluorine-containing polymer obtained in Synthesis Example 3 above was used.

When this molded product was subjected to a color development test in the same manner as in Example 1, no difference was observed between the molded product and the molded product that had not been subjected to humidification and heat treatment.

Comparative Example Polyurethane resin 10 parts, 6-2) [7-8-Methoxy-1+, 3t.

Mix 3'-towamethylsubilane UE2H-1-hensoubilane-2,2'-indoline J 0605 parts and 100 parts of dimethylacetamide, cast the solution on a quartz plate, and dry under a nitrogen stream at 65°C overnight. A photochromic molded article was prepared. When the same color development test as in Example 1 was conducted, the color density of the heat-treated samples was significantly lower than that of the non-heat-treated samples.

[Effects of the Invention] The present invention has the effect of obtaining a photochromic molded article with excellent weather resistance, chemical resistance, heat resistance, and moisture resistance by employing a polymer having a fluorine-containing alicyclic structure as a material. have

Claims (1)

[Claims] 1. A photochromic molded article comprising an organic photochromic compound contained in a polymer having a fluorine-containing aliphatic ring structure.