JPH0272345A - Photochromic photosensitive material - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a photochromic photosensitive material particularly excellent in weather resistance and dark storage stability.

(Prior art) Conventional photochromic photosensitive materials include, for example, spirooxazine-based photochromic compounds dispersed in a polymer compound and made into a film, or photochromic photosensitive materials on a substrate made of glass or a transparent polymer plate. There are those that are coated with a film of a polymer compound containing a compound, or those that are made into a laminate by sandwiching a transparent polymer film containing a photochromic compound between substrates (Japanese Patent Laid-Open No. 60-205429). However, conventional photochromic laminates containing such spirooxazine compounds have the problem of deterioration due to long-term light irradiation because irreversible deterioration products are easily generated during the coloring/decoloring reaction. In order to prevent this problem, the present inventors first proposed a photochromic photosensitive material with excellent weather resistance in which a triplet quencher (troxy free radical) was added (patent application 62-
No. 259778).

However, although photochromic photosensitive materials containing such nitroxy free radicals have improved weather resistance, in some cases they may turn yellow when stored in a dark place, adversely affecting the color tone of the developed state. Something happened.

(Problem to be solved by the invention) In order to prevent deterioration due to long-term light irradiation, this invention attempts to prevent the yellowing phenomenon that occurs when a photochromic photosensitive material containing nitroxy free radicals is stored in a dark place. .

(Means for Solving the Problems) As a result of various studies to solve the above-mentioned problems associated with photochromic photosensitive materials containing spirooxazine-based compounds, the present inventors have discovered that spirooxazine-based compounds and polymeric substances are the main components. In the photosensitive composition, by containing at least one member selected from the group of hindered amine compounds, phenolic compounds, and nickel complexes together with nitroxy free radicals in the photochromink photosensitive composition, erasure can be achieved. It has been discovered that it is possible to prevent the formation of undesirable compounds during color reaction, thereby preventing deterioration due to long-term light irradiation, and furthermore, preventing the phenomenon of yellowing when stored in the dark, and in order to achieve the present invention. It's arrived.

The present invention will be explained in detail below.

Examples of spirooxazine compounds used in the photochromic photosensitive material of the present invention include the following general formula (1) (where R1, RZ and R3 are substituted or unsubstituted alkyl groups, substituted or unsubstituted alkenyl groups, cyclo It represents an alkyl group or an aryl group, and R2 and R3 may be bonded to each other and cyclized.Also, R1 has another spirooxazine ring via an alkylene group or an arylene group, and the whole is a dimer. R4 may be a hydrogen atom or a compound having 1 to 1 carbon atoms.
5 shows the alkyl group. Rings X and Y represent an optionally substituted hydrocarbon aromatic ring or heteroaromatic ring. Z represents an oxygen atom or a sulfur atom. ) can be mentioned.

In the compound represented by the above formula (1), R1, R2 and R3 are an alkyl group such as an alkyl group having 1 to 28 carbon atoms, an alkoxyalkyl group such as a methoxyethyl group or an ethoxyethyl group, a methoxyethoxyethyl group, n -Alkoxyalkoxyalkyl groups such as butoxyethoxyethyl groups, alkoxyalkoxyalkoxyalkyl groups such as methoxyethoxyethoxyethyl groups, ethoxyethoxyethoxyethyl groups, phenyloxyethyl groups, naphthyloxyethyl groups, p-chlorophenyloxyethyl groups, etc. -ruoxyalkyl group, benzyl group, phenethyl group, p-chlorobenzyl group, which may have a substituent,
Arylalkyl groups which may have substituents such as p-nitrobenzyl group, cycloalkylalkyl groups such as cyclohexylmethyl group, cyclohexylethyl group, cyclopentylmethyl group, allyloxyethyl group, 3-bromoallyloxyethyl group Substituted or unsubstituted alkenyloxyalkyl groups such as, cyanoethyl groups, cyanoalkyl groups such as cyanmethyl groups, hydroxyalkyl groups such as hydroxyethyl groups, hydroxymethyl groups, tetrahydrofuryl groups such as tetrahydrofurfuryl groups, tetrahydrofurylethyl groups, etc. Examples include substituted or unsubstituted alkyl groups such as alkyl groups; Examples include substituted or unsubstituted alkenyl groups such as allyl group and 2-chloroallyl group; phenyl group, p-methylphenyl group, naphthyl group, m-methoxyphenyl group; Examples include substituted or unsubstituted aryl groups such as groups, and cycloalkyl groups such as cyclohexyl and cyclopentyl groups.On the other hand, RZ and R3 are linked to each other to form a cyclohexyl group, cycloheptyl group, etc. You can. Moreover, as R1, an alkylene group,
Also included are compounds in which another spirooxazine ring is bonded via an arylene group to form a dimeric compound as a whole. R4 represents a hydrogen atom; an alkyl group having 1 to 5 carbon atoms such as a methyl group or an ethyl group.

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 having 1 to 6 carbon atoms, alkoxy groups, alkoxycarboxyl groups, methoxysulfonyl groups,
Examples include alkoxysulfonyl groups such as ethoxysulfonyl groups, cyano groups, amine groups, dimethylamino groups, and nitro groups.

In the present invention, the following general formula [■] generally refers to 1. −'−NO←−→〕〉N”−0−
The nitroxy free radical used in the photochromic photosensitive material of the present invention is stable and can be isolated.

Such nitroxy free radicals are specifically represented by the following general formula (II) (wherein R1 is an alkyl group having 1 to 20 carbon atoms or an alkoxyalkyl group, R4 is a hydrogen atom or a methyl group, x ,
y represents an optionally substituted hydrocarbon aromatic ring or a heteroaromatic ring. ) It is more preferable to use spirooxazine compounds represented by:

Triplet quenchers, which can be represented by nitroxy free radicals, are mentioned, and R5, R in the above formula (I[]
Examples of 6 include a substituted or unsubstituted aryl group, a hydrocarbon group in which the carbon atom adjacent to the nitrogen atom is a tertiary carbon atom or a quaternary carbon atom; It also includes cases where a carbon atom adjacent to a nitrogen atom has a substituent and a double bond is formed, and the carbon atom has a substituent such as a 5ee-alkyl group or a tert-alkyl group. Further, R5 and R6 may be bonded to each other to form a ring, and the ring may have a substituent.

These synthetic methods are carried out according to the methods described in "New Experimental Chemistry Course" (Maruzen-Nippon Kagaku Kinyo, Vol. 14, P1594-P1598J).

In addition, bicyclo-based nitroxy radicals which are not oxidized to nitrone by Bredt reaction but remain at the nitroxy radical stage (for example, other nitroxy free radicals include the above-mentioned document P15)
97 listed in Table 7.66 can be used.

As the nitroxy free radical preferably used in the present invention, from the viewpoint of heat resistance and activity persistence, the following are preferable.

Hindered amine compounds are known as light stabilizers, and in addition to this effect, they also have the effect of preventing yellowing when nitroxy free radicals are added.

Such hindered amine compounds have a kenyl group represented by the following general formula ([) in the substituted alkyl group, cycloalkyl group, or Al molecule.

ea and RI9 teeth, Other Hinder The base of doormin Or general formula It may have one or more.

What is shown in

Or, a compound having one or more organic groups represented by the following is used, and among these, preferably, Each represents a substituted alkyl group.

a represents a number from 1 to 40.

What is shown in

Particularly preferred among hindered amine compounds or As a thing, To give a specific example, It is as follows.

(C (In the formula, it is -(CH2), - or substituted or un(C-2) Represents a substituted triazine ring.

n is 1 to 10, b is Represents a number from 1 to 40.

(In the formula, Rtgo is a hydrogen atom, Replacement or non-replacement substituted alkyl group, cycloalkyl group or alkaline Represents a kenyl group.

What is shown in

(C (C HI (C-6) H3 (C-4) (C-7) (C-8) (n=1-20) (n 1-20) (C-9) (C (C -11) (n-1~20) (C-13) (n=1~20) C=0 (C-14) (C LH3[;H3υ th etii Phenolic compounds are known as antioxidants. However, in addition to this effect, it also has the effect of preventing yellowing when nitroxy free radicals are added.

As the phenolic compound, for example, the following general formula (I
X) a group, an optionally substituted amino group, an alkoxy group,
Represents a phenoxy group or a hydroxy group. However, x3 does not represent a hydrogen atom. When X3 represents such a group or atom, XI and X5 do not represent a hydrogen atom, and represent a hindered phenol compound as a whole.

Furthermore, x3 is bonded to another phenolic group with or without an oxygen atom, a sulfur atom, a sulfonyl group, a carbonyl group, or an optionally substituted alkylene group or alkenylene group. It may also represent a group. ), among others, the following general formula (X), (where xl, xZ, X3, x4 and X5 are hydrogen atoms, halogen atoms, optionally substituted alkyl
In the formula, Z represents an oxygen atom, a sulfur atom, a sulfonyl group, a carbonyl group, an optionally substituted alkylene group or an alkenylene group, p represents 0 or 1, and X6.
y, 1, xTIXx9, XIOXll, XIZ and X1
3 represents a hydrogen atom, a halogen atom, or an alkyl group. ) or the following general formula [XI] In addition, in the general formula (X), the optionally substituted alkylene group in Z may have another phenolic group.

Specific examples of such phenolic compounds are as follows.

Indicates a nyl group. ) or represents a hydrogen atom, Ql, Q2,
Q3 and Q4 represent an alkyl group. ] is preferred.

In the general formula CIXI, x3 is the aforementioned hindered amine group (for example, a group such as the general formula (Im) +1
3 Good.

C4Hq(t) (D ■3 113 (Di9) (D-25) (D H H3 (D H - Has the effect of preventing yellowing when radicals are added.

As the nickel complex, the following general formula [XII], CI+
□ C=O H2 (X14.xls and Xlb in the above formula represent an alkyl group having 1 to 10 carbon atoms), or the following general formula (XII[),
υ11 Among these, the phenolic compound having the structural formula (D-27) is particularly preferred.

2. Kel complex is known as a doublet quencher,
In addition to such effects, nitroxyfuri (in the above formula)
17X18x'' and X2G represent a hydrogen atom, an alkyl group, or an alkoxy group.) Specific examples of this nickel complex include the following.

(E (E (E-4) (E) As the polymer substance, the spirooxazine compound,
Any material may be used as long as it has good compatibility with nitroxy free radicals, hindered amine compounds, phenolic compounds, and nickel complexes, is optically transparent, and has excellent film-forming ability, such as polymethyl methacrylate, polystyrene, Examples include polyvinyl acetate, polyvinyl butyral, cellulose acetate, polyvinyl chloride, polyvinylidene chloride, vinyl chloride-vinyl acetate copolymer, polypropylene, polyethylene, polyacrylonitrile, urethane resin, epoxy resin, phenoxy resin, polyester, etc. Among these, polyvinyl butyral is preferred from the standpoint of practicality and safety.

Furthermore, if necessary, it may contain a plasticizer or be crosslinked.

The photochromic photosensitive material of the present invention can be in the form of a film,
This includes those in which a photosensitive layer is formed on a substrate, and those in which a photochromic photosensitive layer is sandwiched between substrates to form a laminate. Examples of the substrate include polyethylene terephthalate, cellulose acetate, polycarbonate, glass, etc., and lamination as necessary. It may be something you have done.

The film thickness of the photochromic photosensitive layer is 0.5 μm to 1 fin,
Preferably, it is used in a range of 10 to 250 μm.

The photochromic photosensitive material of the present invention, in which the photochromic photosensitive layer contains nitroxy free radicals and at least one selected from hindered amine compounds, phenolic compounds, and nickel complexes, can be prepared by: Dissolve in a suitable solvent,
This solution can be obtained by coating a suitable transparent support by casting or using a spinner. In the present invention, the amount of the spirooxazine compound used is 0.1 to
It is used in an amount of 50% by weight, preferably 0.5-20% by weight. If the spirooxazine compound is less than 0.1% by weight, sufficient optical density will not be obtained when the photochromic dye is colored, and if it exceeds 50% by weight, the optical density will remain constant and the cost will increase. Undesirable.

The amount of nitroxy free radical used is in the range of 0.1 to 50% by weight, preferably 0.5 to 20% by weight, based on the polymer material. There is no effect when the nitroxy free radical is less than 0.1% by weight, and 50
Even if the amount is more than 4%, the effect will be constant and the cost will be high, which is not preferable.

Furthermore, other additives, hindered amine compounds,
From the viewpoint of preventing yellowing, phenolic compounds and nickel complexes are preferably used, and among them,
The compound having the structure D-27 is most preferred. Similar to nitroxy free radicals, the amount of these three additives used is 0.1 to 50
% by weight, preferably in an amount of 0.5 to 20% by weight, but it is particularly preferred to use the same amount as the nitroxy free radical.

(Effects of the Invention) In addition to the photochromic compound, the photochromic photosensitive material of the present invention contains nitroxy free radicals in order to improve weather resistance properties. By adding selected compounds, in addition to their respective original effects, these three compounds exhibit the effect of preventing yellowing that occurs when stored in the dark due to the addition of nitroxy free radicals, the result,
Since the dark storage stability is significantly improved, there will be no discoloration even during long-term storage, and the color tone of the developed color will not be adversely affected.

Such photochromic photosensitive materials can be used for light control materials such as light control glass for automobiles and building materials, optical filters, masking materials, light meters, and the like.

(Examples) The present invention will be explained by the following examples and comparative examples, but the present invention is not limited by the following examples.

In each example, dark storage stability was evaluated by examining the presence or absence of yellowing. A constant temperature constant temperature machine was used as a yellowing accelerating device. Regarding the presence or absence of yellowing, the absorbance of light around 450 nm was measured, and those with an absorption peak were determined to have yellowing.

Example-1, Comparative Example-1 [Preparation of photochromic interlayer film] Spirooxazine compound having the following structure [A]
= 1 weight ■%, nitroxy free radical (2,2
, 5,5-tetramethylpiperidinyloxycarboxamide) = 1%, manufactured by Chiha Geigy, having the structure (D-27) as an antioxidant, trade name Irganox 1010 (
Hindered phenolic primary antioxidant) = 1%
, polyvinyl edge seal containing plasticizer: 10% by weight) vehicle (ethanol: toluene: n-butanol = 50
:45:5). The resulting solution was coated onto a glass substrate by casting. After this coating film was dried in a vacuum dryer at 70° C. under reduced pressure for 6 hours, another glass plate was vacuum-pressed onto the photochromink photosensitive layer to produce a laminate photochromink photosensitive material.

Next, Comparative Example 1 was prepared using a photochromic photosensitive material prepared under the same conditions as Example 1 except that the hindered phenol antioxidant was not used.

In order to evaluate the dark storage stability of the materials obtained in Example-1 and Comparative Example-1, a constant temperature machine was used to store the materials at 55°C 0%.
A yellowing acceleration test was performed at RH, and the presence or absence of an absorbance peak around 450 nm was examined to investigate yellowing. As a result, yellowing started in Comparative Example-1 within 20 hours, but yellowing did not occur in Example-1 even after 100 hours.

Examples 2 to 3 In the same manner as in Example 1 except that spirooxazine compounds (B) and (C) having the following structures were used,
Photochromic photosensitive materials of Examples 2 and 3 were produced. Example 1 evaluates the dark storage stability of these photosensitive materials.
The presence or absence of yellowing was examined in the same manner as in Example 1.
and the results of Comparative Example 1 are shown in Table 1.

However, B) represents a mixture of a compound where R''=H, R8=C)l:+ and a compound where R1=CI(3, R'=H) at a ratio of 1:1.

Comparative Examples 2 and 3 In Examples 2 and 3, photosensitive materials were prepared in the same manner as in Example 2 and 3, except that no antioxidant (Irganox 1010) was used, and the dark storage stability was was evaluated. The results are shown in Table 1 together with Examples 2 and 3.

Example-4 In Example-1, the above structural formula (D
-27), Cyasorb UV- having the structure of the above structural formula (E-4) as a doublet oxygen quencher
A laminate photochromic photosensitive material was prepared in the same manner except that 1084 (trade name, manufactured by ACC) = 1% by weight was used.

The dark storage stability of the obtained photosensitive material was evaluated in the same manner as in Example-1, and as in Example-1, no yellowing occurred even after 100 hours.

Examples 5 and 6 In Examples 2 and 3, the above structural formula (E-4) was used as a doublet oxygen quencher instead of the antioxidant (D-27).
Photochromic photosensitive materials of Examples 5 and 6 were prepared in the same manner as in Examples 2 and 3, except that 1% by weight of Cyasorb UV1084 (trade name, manufactured by ACC) having the structure was used. These dark storage properties were evaluated in the same manner as in Examples 2 and 3, and the results are shown in Example-
Table 1 shows the results of 4.

Example-7 In Example-1, the above structural formula (D
Mark having the structure of the above structural formula (C-13) as a hindered amine light stabilizer instead of -27)
LA-57 (trade name, manufactured by Adeka Argus); A laminate photochromic photosensitive material was prepared in the same manner as in Example 1 except that 1% by weight was used. The dark storage stability of the obtained photosensitive material was evaluated in the same manner as in Example-1.
Similar to Example-1, no yellowing occurred even after 100 hours.

Example-8 In Examples-2 and 3, instead of the antioxidant (D-27), MarkLA-57 (trade name: ADEKA) having the structure of the above structural formula (C-13) was used as a hindered amine light stabilizer. (manufactured by Argus): Examples 8 and 9 in the same manner as in Examples 2 and 3 except that 1% by weight was used.
A photochromic photosensitive material was created. Evaluation of these dark storage properties was carried out in the same manner as in Examples 2 and 3, and the results are shown in Table 1 together with the results of Example 7.

Examples 10 to 37 A spirooxazine compound having the structural formula CB) in Example 2 above was used as the photochromink compound, the nitroxy free radicals shown in Table 2 below were used, and an antioxidant was used. A laminate was produced in the same manner as in Example 1, except that only one of the compounds shown in Table 2 was used as the (phenol compound), doublet quencher and Keckel complex) or light stabilizer (hindered amine compound). A photochromic photosensitive material was prepared, and its dark storage stability was evaluated in the same manner as in Example-1. The results are shown in Table-2.

Examples 38 to 48 The spirooxazine compound of the structural formula (B) in Example 2 was used as the photochromink compound, and those shown in Table 3 below were used as the nitroxy free radicals, and antioxidants were used. agent (phenolic compound)
, - doublet quencher (Keckel complex) or light stabilizer (hindered amine compound) as shown in Table 3, except that the amounts used of these two types were limited to 0.5% by weight each. A laminate photochromic photosensitive material was produced in the same manner as in Example 1, and its dark storage stability was evaluated in the same manner as in Example-1. The results are shown in Table-3.

Examples 49 to 51 In Example-1, as a photochromic compound,
Using the spirooxazine compound of the structural formula CB) in Example 2, the additives were an antioxidant (phenol compound) shown in Table 3 below, - doublet quencher and Sogal complex), and a light stabilizer. A laminate photochromic photosensitive material was prepared in the same manner as in Example-1 except that 0.4% by weight of each (hindered amine compound) was used, and the dark storage stability was evaluated in the same manner as in Example-1. went.

The results are shown in Table-3.

Claims (1)

[Claims] (1) In a photochromic photosensitive material consisting of a photosensitive composition containing a spirooxazine compound and a polymeric substance as main components, the photochromic photosensitive composition contains a nitroxy free radical as well as a hindered amine compound, a phenol compound and A photochromic photosensitive material characterized by containing at least one member selected from the group of nickel complexes.