JPH0297440A - Intermediate film for photochromic laminated glass - Google Patents

Abstract

PURPOSE:To form the photochromic laminated glass having excellent weatherability by limiting the content of S in the intermediate film for photochromic laminated glass at the time of forming the intermediate film by laminating a photochromic layer on a polyvinyl acetal intermediate film. CONSTITUTION:The intermediate film contg. <=50ppm S element is used as the polyvinyl acetal intermediate film for the photochromic laminated glass formed by laminating the photochromic layer consisting of a photosensitive compsn. essentially consisting of a spirooxazine compd. and a high-polymer material to the whole or part of the film. The high-polymer material which forms the photochromic layer may be the material which has good compatibility with the spirooxazine compd., is optically transparent and has excellent film formability. For example, polyvinyl acetal is exemplified as with the intermediate film and above all, polyvinyl butyral is more preferable. The material contg. <=50ppm S element is further preferable as with the intermediate film.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to an interlayer film for photochromic laminated glass that has particularly excellent weather resistance.

(Prior Art) Recently, vehicle-mounted light control materials using optically variable materials, particularly photochromic materials, have been proposed.

Among such photochromic materials, spirooxazine compounds absorb ultraviolet light of 360 to 3♂o nm and develop a blue color, and when the ultraviolet light is blocked, they return to their original colorless state, repeating the transition between colorless and blue. It has excellent properties and is considered promising.

In addition, as a photochromic automotive light control material, a transparent polymer film having a photochromic photosensitive layer containing a photochromic material is carved between transparent glass substrates.
Polyvinyl butyral is generally used as the polymer film, although it may be made into a laminate.

(Problem to be solved by the invention) However, since sulfuric acid is used as a catalyst during the production of ordinary polyvinyl butyral membranes, the residual S element in the product cannot be avoided, and polyvinyl butyral membranes are usually , contains a considerable amount of S elements.

Conventionally, when polyvinyl butyral is used as an interlayer film for laminated glass, no particular adverse effects due to the residual S element have been found.A- However, in the case of the photochromic material used in the present invention, the residual S element is a component of the spirooxazine compound. There is a problem that it adversely affects the color development retention rate and accelerates the deterioration of weather resistance.

(Means for Solving the Problems) The present invention provides a photochromic layer in which a photochromic layer made of a photosensitive composition containing a spirooxazine compound and a polymeric substance as main components is laminated on all or part of a film. In the polyvinyl acecool interlayer film for glass, the gist is to use an interlayer film having an S element content of 5099 m or less.

The present invention will be explained in detail below.

The spirooxazine compound used in the present invention has the following general formula [.I] (R1, R2 and R3Vi in the formula, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group,
Indicates a cycloalkyl group or an aryl group R2 and R3
may be bonded to each other and cyclized. R4 represents a hydrogen atom or an alkyl group having 1 to 1 carbon atoms. R1 may have another spirooxazine ring via an alkylene group or an arylene group to form a λ-mer compound as a whole. Rings X and Y represent an optionally substituted hydrocarbon aromatic ring or heteroaromatic ring. Z represents an oxygen atom or a sulfur atom. ) is used.

In the compound represented by the above formula [1], R', I(
2 and R3 are an alkyl group such as an alkyl group having a carbon number of up to 2 g, an alkoxyargyl group such as a methoxyethyl group or an ethoxyethyl group, a methoxyethoxyethyl group, n
- Substitution of alkoxyalkoxyalkyl groups such as butoxyethoxyethyl groups, alkoxyalcokynealkoxyalkyl groups such as methoxyethoxyethoxyethyl groups and ethoxyethoxyethyl groups, phenyloxyethyl groups, naphthyloxyethyl groups, ap-chlorophenyloxy/ethyl groups, etc. Aryloxyalkyl group, benzyl group, phenethyl group, r)-chlorobenzyl group, p-
an optionally substituted alkyl group such as nitrobenzyl, a cycloalkylalkyl group such as a cyclohexylmethyl group, a cycloakylethyl group, a cyclopentylmethyl group, an allyloxynethyl group, a 3-bromoallyloxyethyl group, etc. Optionally substituted alkenyloxyalkyl groups, ananoethyl groups, cyanoalkyl groups such as cyanmethyl groups, hydroxyalkyl groups such as hydroxyethyl groups and hydroxymethyl groups, and tetrahydrofuryl alkyl groups such as tetrahydrofurfuryl groups and tetrahydrofurylethyl groups. Substituted or unsubstituted alkyl groups such as groups; substituted or unsubstituted aryl groups such as allyl groups, naphthyl groups, m-methoxyphenyl groups; cycloalkyl groups such as nclohexyl groups and cyclopentyl groups. Further, R2 and R3 may be connected to each other to form a ring such as a cyclohexyl group, a cyclopentyl group, or a cycloheptyl group. Further, as R1, another spirooxazine ring is bonded via an alkylene group or an arylene group,
Also included are compounds that form a λ-mer compound as a whole. R4 represents a hydrogen atom, a methyl group, an ethyl group, or an alkyl group having a carbon number/Nj-.

Examples of the optionally substituted hydrocarbon aromatic ring or heteroaromatic ring of rings X and Y include a benzene ring, a naphthalene ring, a quinoline ring, and a phenanthrene ring. Substituents for these rings include a chlorine atom, Halogen atoms such as bromine atoms and iodine atoms, alkyl groups with carbon number/-4, alkoxy groups, alkoxycarbonyl groups, methoxysulfonyl groups,
Examples include alkoxysulfonyl groups such as ethoxyel and nyl groups, cyano groups, amino groups, dimethylamino groups, and nitro groups.

In the present invention, the general formula [■] of the spirooxazine compound represented by the above formula [■] (in the formula, R1 is an alkyl group or an alkoxyalkyl group having carbon number/-20, and R4 is a hydrogen atom or It is preferable to use a spirooxazine compound represented by a methyl group, X and Y each representing an optionally substituted hydrocarbon aromatic ring, or a heteroaromatic ring.

The intermediate film used when laminating the photochromic photosensitive layer is a polyvinyl acecool film, preferably a polyvinyl butyral film commonly used for laminated safety glass. In this case, the interlayer film used in the present invention is S to improve the weather resistance of the primary chromic compound.
The content of elements! ;0LJprn or less is required.

Such an intermediate film having a low content of S element can be obtained by appropriately selecting reaction conditions and the like during manufacturing.

Further, the polyvinyl acecool interlayer film may contain a plasticizer, if necessary.

Examples of the Q2 agent include phthalates such as diptylphthalate and dioctyl phthalate,
Examples include adipate-based plasticizers such as dioctyl adipate, phosphate-based plasticizers such as tricresyl phosphate, ethylene glycol diester-based plasticizers such as triethylene glycol hexanoate, and mixtures thereof.

In addition, the polymeric substance forming the photochromic layer may be one that is compatible with the spirooxazine compound, is optically transparent, and has excellent film-forming ability; for example, like the intermediate film, polyvinyl Among them, polyvinyl butyral is preferred. If necessary, it may contain a plasticizer or be crosslinked. Also, like the intermediate film, the S element content is J' (7p
pm or less is again preferred. Incidentally, as the plasticizer, the same one used for the above-mentioned intermediate film is used.

In the present invention, the spirooxazine compound is 0.0% relative to the polymeric substance. /˜SO by weight, preferably in an amount of OJ˜20 by weight. The spirooxazine compound is 0. If the amount is less than 50% by weight, sufficient optical density cannot be obtained when colored, and if the amount exceeds 50% by weight, no improvement in optical density is observed and the cost increases, which is not preferable.

If necessary, a light emission improving agent such as a hindered amine compound, an antioxidant, or a nitroxy free radical may be added to the photochromic photosensitive layer. As an additive,
Especially the special application 1986-2! 77r, preferably 0.3-.2% by weight, preferably 0.3-.2
Used at 0% by weight.

The interlayer film for photochromic laminated glass of the present invention is -
For example, a spirooxazine compound and a polymeric substance are dissolved in an appropriate solvent, and this solution is mixed with an S element content of 5.
0 ppm or less of polyvinyl butyral (hereinafter referred to as PV
(abbreviated as B)) can be obtained by coating the entire or part of the intermediate film using screen printing, casting, a spinner, or the like. In this case, the P used
The VB interlayer film may or may not be embossed.

The film thickness of the photochromic layer is r6o, jμ to /thin, preferably to-xsoμ.

(Function) The interlayer film for photochromic laminated glass of the present invention has significantly improved weather resistance. This effect seems to be due to the fact that by using an interlayer film containing the S element in an amount of jθ ppm or less, there was less adverse effect on the spirooxazine compound and the rate of decomposition was reduced.

〔Example〕

The present invention will be specifically explained with reference to the following examples, but the present invention is not limited to these examples in any way.

[Example-1]

A spirooxazine compound having the structure described above (a mixture of 1:/ of a compound where R2=H), as an additive, 2,2. !
, 6-titramethyl-l-pyrrolidinyloxy-3-carboxamide: 2. I fi quantity, plasticizer (triethylene glycol dicoethylbutyrate): /,
/wt cl) 6% by weight of PVB containing 30 ppm S element was dissolved in a solvent (ethanol: toluene 20-butanol = ro2≠j: yo). The obtained solution was printed on a PVB interlayer film with an S element content of 30 pprrl using a screen printing method, and after air drying, two 2M thick sheets were printed.
The photochromic photosensitive material was sandwiched between two clear glass plates and vacuum-pressed to produce a laminated photochromic photosensitive material having a layer of 7 otochromic compounds between the substrates.

The S element was analyzed using fluorescent X-rays (He path, voltage rOKV, current vOmA). The S content was calculated from the STD strength of o, t% polystyrene, and is an approximate value.

[Weather resistance test]

In order to evaluate the weather resistance of these samples, the initial coloring performance was measured using a xenon lamp, and then light irradiation was performed in a xenon fade meter, and the coloring performance was maintained at 70% of the initial value even after irradiation. Ta.

[Comparative example-/]

Next, as a PVB interlayer film, the content of S element is 70 ppm.
A photosensitive material (Comparative Example 1) was produced under the same conditions as in Example except that an intermediate film having the following properties was used.

[Weather resistance test]

Weather resistance was evaluated in the same manner as in Example 1, and the coloring performance was 10% of the initial value after 100 hours of irradiation.

[Example-1] The content of S element was reduced to tppm by the same method as in Example 1.
A photosensitive material (Example 2) was prepared using the r-' V B interlayer film, and a weather resistance test was conducted in the same manner as in Example. As a result, the coloring performance remained at the initial value even after 2000 hours of irradiation. ♂O
% of coloring performance was maintained.

(Effects of the Invention) The 7 otochrominoku laminated glass intermediate of the present invention has a significantly lower S element content than the polyvinyl acetal film conventionally used as an interlayer film for laminating photochromic photosensitive layers using spirooxazine compounds. I did, that is!
By limiting the amount to less than Oppm, it is possible to prevent a decrease in the color retention rate of the spirooxazine compound, and by using a vaginal interlayer, a photochromic laminated glass with excellent weather resistance can be manufactured.

These laminated glasses are used for various purposes as optically variable laminated structures.

Claims (1)

[Claims] (1) A polyvinyl acetal interlayer film for photochromic laminated glass in which a photochromic layer made of a photosensitive composition containing a spirooxazine compound and a polymeric substance as main components is laminated on all or part of the film. An interlayer film for photochromic laminated glass, characterized in that an interlayer film having an S element content of 50 ppm or less is used.